Organic Dyes

Photocatalysis with organic dyes: facile access to reactive
intermediates for synthesis

Stephanie G. E. Amos‡, Marion Garreau‡, Luca Buzzetti‡ and Jerome Waser*
Review Open Access
Address: Beilstein J. Org. Chem. 2020, 16, 1163–1187.

Laboratory of Catalysis and Organic Synthesis, Ecole Polytechnique doi:10.3762/bjoc.16.103
Fédérale de Lausanne, EPFL, SB ISIC LCSO, BCH 4306 1015
Lausanne, Switzerland Received: 21 March 2020
Accepted: 11 May 2020
Email: Published: 29 May 2020
Jerome Waser* - [email protected]
This article is part of the thematic issue "Advances in photoredox
* Corresponding author ‡ Equal contributors catalysis".
Keywords: Guest Editor: T. Noël

organic dyes; photocatalysis; photoredox catalysis; radicals; reactive
intermediates © 2020 Amos et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
Organic dyes have emerged as a reliable class of photoredox catalysts. Their great structural variety combined with the easy fine-
tuning of their electronic properties has unlocked new possibilities for the generation of reactive intermediates. In this review, we
provide an overview of the available approaches to access reactive intermediates that employ organophotocatalysis. Our contribu-
tion is not a comprehensive description of the work in the area but rather focuses on key concepts, accompanied by a few selected
illustrative examples. The review is organized along the type of reactive intermediates formed in the reaction, including C(sp3) and
C(sp2) carbon-, nitrogen-, oxygen-, and sulfur-centered radicals, open-shell charged species, and sensitized organic compounds.
Review
Introduction
In the last decade, synthetic organic chemistry has experienced sion of photocatalytic methods [12]. These catalysts typically
the renaissance of photocatalysis. Since the early seminal absorb light in the blue region and promote different activation
reports [1-4], inspired by pioneering works in photochemistry modes, including photoinduced electron transfer (PET) and
[5-7], this field has attracted increasing attention, and organic energy transfer (EnT), which respectively lead to the formation
chemists have developed a wide variety of photocatalytic reac- of open-shell and electronically excited species. These reactive
tions [8-11]. One of the reasons for this rapid growth resides in intermediates are then used to forge new chemical bonds or to
the availability of visible light-absorbing transition metal com- induce structural modifications within the organic substrates.
plexes. These catalysts can harvest the energy of visible-light The versatility of these metal complexes is due to their wide
photons and transfer it to organic molecules, giving access to operational redox windows, which allows them to interact via
key reactive intermediates. For instance, ruthenium and iridium their excited states with different classes of molecules. Howev-
polypyridyl complexes played a central role in the rapid expan- er, the relatively high cost of these photocatalysts, their toxicity,
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Beilstein J. Org. Chem. 2020, 16, 1163–1187.
and the limited abundance of the coordinating transition metals able electron acceptor A or electron donor D. In an oxidative
can hamper their applicability [13]. For these reasons, the quest quenching cycle, PC* acts as a reductant donating an electron
for cheaper, more sustainable, and environmentally benign to A. This generates the oxidized form of the photocatalyst,
photocatalysts is of high importance, and organic dyes repre- PC•+, and a reduced acceptor, A•−. Alternatively, in a reductive
sent a powerful platform for pursuing this goal. quenching cycle, PC* acts as an oxidant promoting an SET oxi-
dation of the electron donor D. This leads to the reduced photo-
The ability of organic dyes to absorb light and promote transfor- catalyst PC•− and the oxidized donor D•+. Following this initial
mations is known since the early stage of photochemistry, and SET, a second electron transfer must occur to ensure the cata-
they represent attractive alternatives to the established transi- lyst turnover and restore the ground state photocatalyst: PC•+
tion metal-based photocatalysts [14-18]. In addition to their needs to be reduced by an electron donor D, whereas PC•−
ready availability and low cost, these molecules are often needs to undergo an oxidation by an electron acceptor A. In
biocompatible, and they can be easily functionalized in order to each of these steps, the role of A or D is assumed by a redox-
modulate their spectroscopical and redox features. active agent, either the substrate, a sacrificial electron donor/
acceptor, or a reactive intermediate. This approach, usually
In the last years, several classes of organic dyes, such as acri- named photoredox catalysis, has known a remarkable growth in
diniums (OD1–4), cyanoarenes (OD5–8), diaryl ketones (OD9/ the last decade and has given access to both neutral and charged
10), flavins (OD11/12), xanthenes (OD13–15), thiazines radical species. The thermodynamic feasibility of these SETs is
(OD16/17) and various other dyes, such as OD18–21, have related to the redox potentials of the species involved. The
been exploited (Figure 1), and the field of organic photocataly- values of the redox potentials discussed in this review are gen-
sis has been extensively covered by various reviews [16,19-25]. erally taken from the original publications described in the cor-
Most of these reports are organized according to the structural responding paragraphs.
features of the dye and/or their applications in synthetic chem-
istry. In contrast, this review will focus on the different possible In the second case (Scheme 1, box 2), the excited photocatalyst
conceptual approaches based on organic photocatalysts for the can engage in an EnT mechanism. Upon the excitation and
generation of reactive intermediates. After a short introduction intersystem crossing, the triplet state photocatalyst 3PC* can
on activation modes in photocatalysis, selected case studies interact directly with a ground state species Sub and transfer the
where organic dyes have been exploited for generating carbon- triplet energy to generate an excited state Sub* and the ground
centered radicals, charged open-shell species, and heteroatom- state PC. In most cases, Sub* is in the triplet state if it is an
centered radicals will be covered. The last short section will be organic molecule. A common exception to this is molecular
devoted to activated organic substrates generated by energy oxygen, which upon excitation attains a more reactive singlet
transfer. C(sp) radicals will not be discussed. To the best of our state.
knowledge, no report on an organophotocatalyzed generation of
a C(sp) species has been disclosed yet. Each presented ap- In the third mode of activation, atom transfer (AT, Scheme 1,
proach will be accompanied by one selected example, which we box 3), the excited state photocatalyst PC* can abstract an
found particularly illustrative. This report is therefore in no atom, typically hydrogen, from a suitable substrate Sub-X,
means comprehensive, and readers searching to gain deeper leading to the direct formation of an open-shell species, Sub•. In
insight into photocatalytic processes and/or for an exhaustive this case, the catalytic cycle is closed by a subsequent atom
coverage of applications should refer to more complete special- transfer that restores the ground state photocatalyst PC.
ized reviews and books [26-30]. We hope this report can moti-
vate general synthetic chemists to consider photocatalytic ap- C(sp3) radicals
proaches mediated by organic dyes as valuable tools for Carbon-centered sp3 carbon (C(sp3)) radicals are important
accessing important reactive intermediates and guide them in reactive intermediates for the construction of C–C and
the first choice of a catalyst and a method. C–heteroatom bonds [31]. Their addition onto unsaturated
systems, such as olefins and arenes, is particularly efficient. Ad-
Activation modes in photocatalysis ditionally, alkyl radicals can undergo translocations, abstracting
Electronically excited photocatalysts interact with organic mol- atoms from different sites. Recently, the ability of transition
ecules via three main pathways: electron transfer (ET), EnT, metal complexes to intercept alkyl radicals has been exploited
and atom transfer (AT). for expanding the possibility of C–C bond formation reactions
to cross-couplings. In all of these transformations, the substitu-
In the first case (Scheme 1, box 1), the excited photocatalyst ents on the alkyl radical determine if it reacts as a nucleophile
(PC*) undergoes a single-electron transfer (SET) with a suit- or an electrophile [32].
1164
Figure 1: Selected examples of organic dyes. Mes-Acr+: 9-mesityl-10-methylacridinium, DCA: 9,10-dicyanoanthracene, 4CzIPN: 1,2,3,5-
tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, 4DPAIPN: 1,3-dicyano-2,4,5,6-tetrakis(N,N-diphenylamino)benzene, PHTH: 10-phenylphenothiazine,
dArBPTH: 10-([1,1'-biphenyl]-4-yl)-3,7-bis(4-butylphenyl)-10H-phenothiazine, Py-BTz-Py: butyl-4,7-bis(1-methyl-1H-pyrrol-2-yl)-2H-benzo[d][1,2,3]tri-
azole, PDI: N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-bis(dicarboximide).
1165
Scheme 1: Activation modes in photocatalysis.
Recently, photoredox catalysis has emerged as a powerful tool cals from carboxylic acids relies on the oxidation of the CO2H
to access C(sp3) radicals, and organic dyes (ODs) have been group. However, the high oxidation potential of these species
demonstrated to act as competent photocatalysts for these light- makes them difficult to be directly activated by the excited state
mediated reactions. The main strategies used include decarbox- photocatalyst. For these reasons, the photocatalyzed decarbox-
ylations from carboxylic acid derivatives (CO 2 X), such as ylation often proceeds on the corresponding carboxylates,
carboxylates or RAEs (Redox Active Esters), oxidative frag- which are easier to be oxidized. This photoinduced SET, fol-
mentations, and reductive fragmentations of various redox- lowed by the loss of CO2 as the sole byproduct, gives access to
active groups (X) as well as hydrogen atom abstractions the desired C(sp3) radicals. Organic dyes are competent photo-
(Scheme 2). catalysts for these transformations, with many reports having
appeared in the last five years.
For example, Nicewicz developed a photocatalytic hydrodecar-

boxylation of primary, secondary, and tertiary carboxylic acids
in 2015 (Scheme 3) [41]. The use of the strong oxidant Mes-
Acr-Ph+ (OD3, E(PC+*/PC) ≈ 2 V) as organic photocatalyst
leads to the oxidation/decarboxylation of the in situ-generated
carboxylates (Eox ≈ 1.3 V). An organic disulfide cocatalyst,
(PhS)2, activated by the reduced photocatalyst, was found to act
as a co-base (PhS−) and a hydrogen atom source (PhSH). The
reaction allows the direct conversion of carboxylic acids, e.g.,
Scheme 2: Main strategies for the formation of C(sp3) radicals used in

organophotocatalysis.
Decarboxylation
Carboxylic acids are naturally abundant functionalities that
provide an easy access to C(sp3) radicals. Since the dawn of
organic chemistry, several radical decarboxylations have been
developed, including the Kolbe electrolysis [33,34], the Huns-
diecker reaction [35], and the Barton decarboxylation [36-38].
More recently, photoredox catalysis has appeared as a mild al-
ternative to these venerable transformations [39,40], allowing Scheme 3: Illustrative example for the photocatalytic oxidative genera-
the smooth generation of alkyl radicals from carboxylic acid de- tion of radicals from carboxylic acids: the hydrodecarboxylation re-
ported by Nicewicz and co-workers [41].
rivatives. One of the main strategies for accessing C(sp3) radi-
1166
3.1 to the corresponding alkanes, e.g., 3.2. The scope includes which undergoes a radical conjugate addition with a suitable
carboxylic acids that were previously recalcitrant to other oxi- Michael acceptor 4.2, providing the desired alkylation products
dative photocatalytic decarboxylations due to their high oxida- 4.3.
tion potential.
A similar strategy for radical generations was applied by
Other organic dyes, including several acridinium salts, have Glorius and co-workers. They exploited a combination of
been successfully applied in organophotocatalytic decarboxyl- organophotoredox and copper catalysis to achieve the conver-
ation protocols. For example, rhodamine 6G (OD14, sion of carboxylic acids into alkenes using N,N-diaryldihy-
E(PC + */PC) ≈ 1.2 V) [42] was used for the photocatalytic drophenazine as an organic photocatalyst [46]. Rose bengal
decarboxylative azidation of cyclic amino acids and rose bengal (OD15) was also exploited as an organic photocatalyst to
(OD15) [43] for a decarboxylative amination of indoline-2- trigger the reductive fragmentation of phthalimide-based redox-
carboxylic acids with azodicarboxylate esters. active esters [47].
Another photocatalytic strategy for accessing C(sp3) radicals Other oxidative fragmentations
from carboxylic acids proceeds through a reductive decarboxyl- In addition to the decarboxylation reactions, organic photoredox
ation pathway. This approach relies on the conversion of the catalysis can be exploited to access C(sp3) radicals via the oxi-
acid into an easy reducible moiety, such as a redox-active ester dative fragmentation of different redox-active functional groups
(RAE). These species can accept one electron from the photo- (Figure 2) [48]. Among them, dihydropyridines (DHPs), sili-
catalyst, and the ensuing reduced species releases the corre- cates, and tetrafluoroborate salts were recently exploited in
sponding C(sp3) radical after a fragmentation and CO2 loss. organophotocatalytic reactions. These functionalities can act as
This approach represents an alternative to oxidative decarboxyl- donors in reductive quenching manifolds and release the desired
ations, allowing the design of a photocatalytic cycle based on C(sp3) radicals after the fragmentation of the oxidized form.
the SET reduction of the substrate. Furthermore, the relatively Due to their attitude towards SET oxidations, these substrates
low reduction potential of these species (E red ≈ −1.1 V for are valuable alkyl radical precursors; however, they are general-
N-acetoxyphthalimide) [44] brings them into the operational ly less available than carboxylic acids, and the fragmentations
range of various organic dyes, allowing mild reaction condi- release stoichiometric amounts of byproducts.
tions.
König reported a visible light-promoted photochemical reduc-

tive decarboxylation/alkylation of carboxylic acid analogs
(Scheme 4) [45]. In this protocol, the carboxylic acids are con-
verted into the corresponding RAE 4.1 by a condensation with
N-hydroxyphthalimide. The organic dye eosin Y (OD13,
E(PC/PC−) ≈ −1.1 V), in the presence of the sacrificial electron
donor DIPEA, can reduce these species under green light irradi-
ation. The ensuing decarboxylation provides a C(sp3) radical, Figure 2: Common substrates for the photocatalytic oxidative genera-
tion of C(sp3) radicals.
The organic dye 4CzIPN (OD6), due to its oxidative abilities in

the excited state (E(PC*/PC−) ≈ 1.35 V), has proved to be a
versatile organic photocatalyst for accessing C(sp3) radicals
through oxidative fragmentations. In particular, it has been used
for generating an alkyl radical from the 4-alkyl-1,4-dihydropyri-
dine (DHP) 5.1 in a metallaphotoredox protocol for the synthe-
sis of alkylated (hetero)arenes (Scheme 5a) [49]. These sub-
strates, easily synthesized from the corresponding aldehydes,
can undergo a facile SET oxidation with the excited state of
4CzIPN. The ensuing fragmentation of the pyridyl group
Scheme 4: Illustrative example for the photocatalytic reductive genera- releases the C(sp3) radical, which is intercepted by an organo-
tion of C(sp3) radicals from redoxactive esters: the decarboxylative metallic intermediate, obtained by the oxidative addition of a
Giese reaction reported by König and co-workers [45].
nickel catalyst to the (hetero)aryl bromide 5.2. The desired
1167
(hetero)arene product 5.3 is obtained after the reductive elimi-

nation of the nickel complex. In this method, the reduced
organic photocatalyst (E(PC/PC−) ≈ −1.2 V) is responsible for
turning over the nickel catalytic cycle by reducing the Ni(I)
intermediate.
Scheme 6: Illustrative example for the photocatalytic oxidative genera-

tion of C(sp3) radicals from trifluoroborates: the addition to quinolines
reported by Molander and co-workers [51].
Other reductive fragmentations

Another organophotocatalytic strategy for accessing C(sp3)
radicals relies on the reductive homolytic cleavage of easily
reducible functional groups. In this case, the substrates can act
as acceptors in SET reductions, and the alkyl radical is ob-
tained after the fragmentation of the reduced intermediates. Due
to their availability and their attitude to undergo reductive frag-
mentations, alkyl halides have been extensively used as C(sp3)
radicals sources.
Scheme 5: Illustrative example for the photocatalytic oxidative genera-

tion of radicals from dihydropyridines and silicates: the nickel-cata- Recently, Dell’Amico and co-workers reported a new class of
lyzed cross-coupling with aryl bromides and addition to imines re- naphthochromenone-based organic dyes, which, due to the wide
ported by Molander and co-workers [49,50].
redox window (E = 3.22 eV, +1.65 V/−1.77 V), can be
exploited as photocatalysts for various transformations, includ-
Organosilicates can also be exploited as alkyl radical sources in ing the reductive dehalogenation of benzylic halides (Scheme 7)
organic photocatalytic reactions. For example, Molander and [52]. In this protocol, the excited state photocatalyst OD18 can
co-workers developed a photochemical protocol for the radical generate C(sp 3 ) radicals through the reductive cleavage of
alkylation of imines using ammonium alkylbis(catecholato)sili- various benzyl halides 7.1 (I, Br, Cl). The radical is then inter-
cates 5.4 as the C(sp3) radical precursors (Scheme 5b) [50]. cepted by an H atom donor (Hantzsch ester), which delivers the
4CzIPN (OD6) was found again to be the best organic photocat- corresponding toluene derivative 7.2.
alyst, triggering the oxidative fragmentation of the bis(cate-
cholato)silicate. The so-formed alkyl radical adds to the imine
substrate 5.5, yielding the desired amine product 5.6.
Finally, the same group developed a photochemical radical

alkylation of heteroarenes with alkyl trifluoroborate salts
(Scheme 6) [51]. In this reaction, the photoinduced oxidative
fragmentation of the alkyl trifluoroborate salt 6.1 was promoted
by the acridinium photocatalyst OD2. The resulting alkyl
radical can be intercepted by a protonated heteroarene 6.2. The
addition of potassium persulfate leads to the regeneration of the Scheme 7: Illustrative example for the photocatalytic reductive genera-
photocatalyst and the rearomatization of the intermediate, deliv- tion of C(sp3) radicals from benzylic halides: the reduction with a
Hantzsch ester reported by Dell’Amico and co-workers [52].
ering the desired alkylated heteroarene 6.3.
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Other organic dyes can promote the reductive fragmentation of In this report, the excited state of a push–pull benzophenone
alkyl halides. For instance, König and Zeitler demonstrated that OD10 can abstract an H atom from the substrate tetrahydro-
a combination of eosin Y (OD13) with a sacrificial electron furan (8.1), giving access to the key C(sp3) radical. The nickel
donor can trigger the reductive debromination of several α-car- catalyst, after an oxidative addition with the aryl bromide 8.2
bonyl halides [53]. Riboflavin (OD11) [54] and thiaporphyrin and intercepting the alkyl radical species, gave the radical cross-
[55] have been applied as well as organic photocatalysts for coupling product 8.3 upon a reductive elimination.
similar reductive dehalogenations.
Other diaryl ketone dyes, such as 9-fluorenone, have been suc-
Hydrogen atom transfer cessfully employed for the generation of C(sp3) radicals via
Photocatalytic hydrogen atom transfer (HAT) represents a valu- HAT [58]. Interestingly, Wu and co-workers demonstrated that
able strategy for accessing C(sp3) radicals. This method allows eosin Y (OD13) can also act as a direct HAT catalyst under
the direct cleavage of a C–H bond and the consequent genera- visible-light irradiation [59]. Organic photoredox catalysis can
tion of alkyl radicals without relying on the presence of redox- also drive indirect HAT processes. In these reactions, the
active functional groups. This results in a superior atom excited state of the photocatalyst engages in SET or energy
economy compared to other methods for radical generation transfer events with suitable cocatalysts for hydrogen shuttling,
[56]. Within this field, organic dyes can act as competent photo- such as thiols. This results in the formation of active species
catalysts for direct HAT processes. Specifically, upon light ex- that promote the H abstraction from the substrates. MacMillan
citation, photoactive carbonyl compounds, such as benzo- exploited this strategy for the deuteration and tritiation of bio-
phenone and its derivatives, reach an electronically excited logically relevant compounds using D2O and T2O as hydrogen
triplet state: a biradical capable of abstracting an H atom from isotope sources (Scheme 9) [60]. The SET oxidation of the thiol
C–H bonds. Recently, Martin exploited this feature in a nickel- cocatalyst 9.2, triggered by the excited photocatalyst 4CzIPN
catalyzed process for the alkylation of arenes (Scheme 8) [57]. (OD6), generates a sulfur-centered radical capable of driving
the HAT process with the substrate 9.1. The trapping of the
ensuing C(sp3) radical with the deuterated or tritiated thiol
results in the incorporation of deuterium or tritium in multiple
positions within the product 9.3.
C(sp2) radicals
Aryl radicals
Considering the importance of arylation reactions in organic
synthesis [61], aryl radicals are important intermediates to
Scheme 8: Illustrative example for the photocatalytic generation of develop new synthetic methods [62]. Their reactivity was first
C(sp3) radicals via direct HAT: the cross-coupling with aryl bromides explored in the Meerwein arylation as well as the
reported by Martin and co-workers [57].
Gomberg–Bachman and the Sandmeyer reaction [63-65]. Simi-
Scheme 9: Illustrative example for the photocatalytic generation of C(sp3) radicals via indirect HAT: the deuteration and tritation of C–H bonds re-
ported by MacMillan and co-workers [60].
1169
lar to C(sp3) radicals, aryl radicals add to unsaturated systems, key aryl radical was trapped with heteroarenes, such as 11.2, to
such as (hetero)arenes, alkenes, or alkynes. They can also give the arylation products 11.3. Recently, similar methodolo-
perform atom abstractions, in particular HATs and halogen gies for aryl radical generations have been developed exploiting
abstractions [66]. The generation of such species generally flow techniques [74] and different organophotocatalysts, such
occurs through the homolytic cleavage of a peripheral σ bond as a metal-free porphyrin [75] and rhodamine 6G (OD14) [76].
[67,68]. In the majority of the cases, a leaving group is reduced
and fragments to the aryl radical. The precursors of choice Aryl radicals from aryl halides. Aryl halides are generally
encompass aryl diazonium salts, haloarenes, and sulfur(IV) or more difficult to reduce than aryl diazonium salts
sulfur(VI) compounds (Scheme 10). (Ered < −1.2 V) [77,78]. However, they are more available and
bench-stable. Their reduction potential is dependent on the sub-
stitution pattern and on the nature of the halide: as a trend, aryl
iodides are easier to reduce than aryl bromides and aryl chlo-
rides [67,77]. Under organophotocatalytic conditions, the reduc-
tion can be achieved following two main strategies for
accessing stronger reduction potentials: (a) tuning the elec-
tronics of the organic dye or b) tuning the stability of the
reduced photocatalyst, allowing a second photoexcitation.
For an example of the first strategy, Zhang and co-workers de-

Scheme 10: Selected precursors for the generation of aryl radicals signed a new photocatalyst: Py-BTz-Py (OD19, Scheme 12),
using organophotocatalysis.
which was reducing enough (E(PC•+/PC*) ≈ −2.0 V) to acti-
vate the aryl iodides 12.1 for the synthesis of the arylated
Aryl radicals from aryl diazonium salts. Aryl diazonium salts heteroarenes 12.3 via an intermolecular process [79]. Alemán
are attractive substrates for accessing aryl radicals. Despite their and co-workers used PHTH (OD16) for the synthesis of various
intrinsic thermal instability and exothermic decomposition heteroatom-containing bicycles 12.4 through a tethered electro-
[69,70], these species are straightforward to synthesize and can phile approach [80].
be easily reduced (Ered ≈ −0.1 V to −0.3 V) [71,72]. This makes
them valuable electron acceptors for photocatalytic strategies.
The SET reduction results in the generation of an aryl radical
upon the irreversible loss of N2 as the sole byproduct. As first
reported by König and co-workers, organic dyes can be success-
fully employed as photocatalysts for accessing aryl radicals
from these substrates [73]. In this work (Scheme 11), eosin Y
(OD13) was used for the organophotocatalytic reduction of the
aryl diazonium salts 11.1 under visible-light irradiation. The
Scheme 12: Illustrative examples for the photocatalytic reductive gen-

eration of aryl radicals from haloarenes: the photocatalytic heteroaryla-
tion of arenes reported by Zhang and co-workers (top) [79] and the
intramolecular heterobicycle synthesis reported by Alemán and
co-workers (bottom) [80].
Scheme 11: Illustrative example for the photocatalytic reductive gener- For the second strategy, König and co-workers developed an
ation of aryl radicals from aryl diazonium salts: the photocatalytic organic dye-based consecutive photoinduced electron transfer
Meerwein arylation reported by König and co-workers [73].
(conPET) strategy for the reduction of various aryl halides in
1170
2014 [81]. As depicted in Scheme 13 (box 1), the conPET

mechanism involves a first PET (PET 1 ), where the excited
photocatalyst (PC*) is reduced by a sacrificial electron donor
D, such as a trialkylamine. The ensuing radical anion
(PC •− ), associated to an extended π-system, is persistent
enough to absorb a second photon. The resulting excited state
of the radical anion (PC • − *) is a strong reductant
(E(PC/PC •− *) < −1.5 V), which can reduce the electron
acceptor (A), resulting in a second PET (PET 2 ). With this
strategy, the authors could reduce a broad variety of aryl halides
13.1 using N,N-bis(2,6-diisopropylphenyl)perylene-3,4,9,10-
bis(dicarboximide), (PDI, OD20) as a conPET photocatalyst for
Scheme 14: Illustrative example for the photocatalytic reductive gener-
the generation of an aryl radical (box 2). The latter could be ation of aryl radicals from arylsulfonyl chlorides: the phenanthridine
hydrogenated or heteroarylated to give the desired dehalo- synthesis via aryl radical addition to isonitriles reported by Gu and
co-workers [85].
genated products 13.3 or arylheteroarenes 13.4. Other organic
dyes, such as dicyanoanthracene (OD5) and rhodamine 6G
(OD14), have been successfully used in similar conPET strate- The direct organophotocatalytic activation of the C–H bond of
gies for the aryl radical-mediated derivatization of aryl bro- an arene represents an atom-economical and attractive strategy
mides [82,83]. A similar double SET approach, where the first for the generation of aryl radicals. Although inaccessible to
reduction of dicyanoanthracene (OD5) is achieved electrochem- date, a two-step strategy was recently developed by the Procter
ically, was recently disclosed by Lambert and Lin. In this group. They reported a one-pot organophotocatalytic strategy
report, the photoexcited radical anion of the dye was exploited for the heteroarylation of nonprefunctionalized arenes
for accessing aryl radicals as intermediates of a reductive bory- (Scheme 15) [87]. First, a triaryl sulfonium salt 15.3 is gener-
lation of aryl halides [84]. ated from the substrate 15.1 using dibenzothiophene S-oxide
(DBTSO, 15.2). Then, under visible-light irradiation, 15.3 could
Other sources of aryl radicals. In addition to aryl diazonium be reduced with PHTH (OD16) to generate an aryl radical that
salts and aryl halides, arylsulfonyl chlorides can be reduced could further be trapped by a heteroarene 15.4, such as pyrrole
with common organic dyes due to their relatively low reduction or thiophene, furnishing the arylation product 15.5.
potential [78]. As an example, Gu and co-workers reported the
use of eosin Y (OD13) for the SET reduction/desulfonylation of Acyl, oxylacyl, and carbamoyl radicals and their
the arylsulfonyl chlorides 14.1 (Scheme 14) [85,86]. The analogues
ensuing aryl radical is trapped by an aryl isonitrile 14.2, The photocatalyzed generation of acyl radicals is of great
affording the bisarylation product 14.3. interest as they are precursors for the synthesis of diverse car-
Scheme 13: Illustrative example for the photocatalytic reductive generation of aryl radicals from aryl halides using a conPET strategy. Box 1: conPET
mechanism and box 2: the dehalogenation and heteroarylation of aryl radicals reported by König and co-workers [81].
1171
that rose bengal (OD15) acts as an energy transfer sensitizer

generating singlet oxygen. The authors proposed that the latter
would be responsible for the H atom abstraction from the α-keto
acid. The α-keto carboxyl radical undergoes a decarboxylation,
leading to the desired acyl radical.
Scheme 15: Illustrative example for the reductive photocatalytic gener-

ation of aryl radicals from triaryl sulfonium salts: the one-pot C–H
heteroarylation of arenes reported by Procter and co-workers [87].
Scheme 17: Illustrative example for the decarboxylative photocatalytic

bonyl compounds [88]. The acyl radical is generally considered generation of acyl radicals from α-keto acids: the photocatalytic acyl-
ation of indole (17.2) reported by Wang and co-workers [89].
as a nucleophilic radical and reacts rapidly with electron-poor
π-systems: heteroarenes and electron-poor alkenes in particular.
Using the tools of organophotocatalysis, this reactive intermedi- Acyl radicals can also be accessed through the oxidative
ate can be directly obtained from carbonyl derivatives, such as cleavage of a redox-active group, such as acylsilanes or 1,4-
aldehydes, α-keto acids, oxalates, or carbamates through oxida- dihydropyridine derivatives. In 2018, Fagnoni and co-workers
tive or reductive decarboxylations, oxidative fragmentation, or developed an organophotocatalytic method to access nonsym-
H-abstraction (Scheme 16). metrical ketones through the oxidation of the alkyl acylsilanes
18.1 (E ox ≈ +1.3 V) by an acridinium photocatalyst OD2
(E(PC+*/PC) ≈ 2.1 V, Scheme 18) [90]. After the fragmenta-
tion, the acyl radical can add to various Michael acceptors 18.2
to afford the desired ketone 18.3.
Scheme 16: Main strategies towards acyl radicals used in organopho-

tocatalysis.
Scheme 18: Illustrative example for the oxidative photocatalytic gener-
ation of acyl radicals from acyl silanes: the acylation of electron-poor
olefins reported by Fagnoni and co-workers [90].
A common way to access such radicals is through the decarbox-
ylation of α-keto acids. Both reductive and oxidative strategies
were implemented. In 2016, Wang and co-workers developed Recently, the Melchiorre group reported a carbamoyl radical-
an organophotocatalyzed acylation of indoles (Scheme 17) [89]. mediated metallaphotoredox synthesis of arylamides
They successfully converted the aryl and alkyl α-keto acids 17.1 (Scheme 19) [91]. In this protocol, excited-state 4CzIPN (OD6)
to the 3-acylindoles 17.3 using rose bengal (OD15) as a photo- oxidizes a 4-carbamoyl-1,4-dihydropyridine 19.1, which then
catalyst under aerobic conditions. Mechanistic studies suggest fragments, releasing the corresponding pyridinium and the
1172
desired carbamoyl radical. The latter can be intercepted by an (NHPI, OD22, similar to the benzophenone photocatalysts OD9
organonickel species resulting from the oxidative addition of and OD10) can abstract an H atom from the aldehyde substrate
the nickel catalyst to the aryl bromides 19.2. The arylamides 20.1. The resulting acyl radical adds to the (E)-β-nitrostyrene
19.3 are obtained following a reductive elimination, and the re- 20.2, and the following denitrosylation affords the chalcones
sulting Ni(I) species is reduced by the photocatalyst, and thus 20.3.
closing the catalytic cycle.
Scheme 20: Illustrative example of the photocatalytic HAT approach

for the generation of acyl radicals from aldehydes: the vinylation of
aldehydes reported by Yadav and co-workers [92].
Alkenyl and aryl radical ions (radical cations

and radical anions)
Scheme 19: Illustrative example for the oxidative photocatalytic gener-
ation of carbamoyl radicals from 4-carbamoyl-1,4-dihydropyridines: the Recently, the exploitation of alkenyl and aryl radical ions has
metallaphotoredox synthesis of aryl amides reported by Melchiorre and emerged as a platform for the functionalization of small mole-
co-workers [91].
cules. They appear as attractive intermediates for a direct alkene
difunctionalization or arene C–H functionalization. In particu-
Finally, Yadav and co-workers developed a method for a chal- lar, radical cations are strong electrophiles and undergo nucleo-
cone synthesis using an H abstraction approach to access an philic additions with two-electron donors (Scheme 21a) [93,94].
acyl radical (Scheme 20) [92]. The authors proposed that the In contrast, radical anions can act as very strong single-electron
excited triplet state of the photocatalyst N-hydroxyphthalimide nucleophiles and are often subject to fragmentation to give a
Scheme 21: General reactivity of a) radical cations; b) radical anions; c) the main strategies towards aryl and alkenyl radical ions used in organopho-
tocatalysis.
1173
neutral free radical and a charged species (Scheme 21b) [77,95]. sulfonic acids) [99]. During these studies, they optimized the
When a fragmentation is not favored, these charged radicals can structure of the Mes-Acr+ dye to improve the catalyst turnover.
be intercepted and lead to different selectivities when compared When changing the group on the nitrogen atom of the acri-
to a traditional two-electron chemistry (e.g., anti-Markovnikov dinium scaffold from an alkyl group (Me in OD2) to an aryl
vs Markovnikov or ipso-SNAr reactions). Heteroatom-contain- group (Ph in OD3), they could limit the photocatalyst bleaching
ing radical anions, such as ketyl radicals, constitute a special due to the demethylation of the organic dye.
class of substrates that usually undergo a protonation to form
C(sp3) radicals. Alkene radical anions have been less exploited than their
cationic equivalents. In 2017, the Lei group developed a
Alkenyl or aryl radical ions are generally accessed through Markovnikov-selective hydrosulfonylation reaction
SET. The presence of electron-donating groups facilitates the (Scheme 23) [100]. The alkynes 23.1 could be successfully con-
oxidation of the precursor to the radical cations, while electron- verted to the vinyl sulfones 23.3 in the presence of the aryl
poor alkynes and arenes can undergo SET reductions to sulfones 23.2 using eosin Y (OD13) as a photocatalyst. A tenta-
generate the corresponding radical anions (Scheme 21c). tive mechanism was proposed by the authors: under visible-
Organophotocatalysis has been successfully exploited to light irradiation, the arylsulfinic acid could be oxidized to the
promote these SETs and access charged alkenyl and aryl radi- corresponding sulfonyl radical by the excited state of eosin Y
cals. The reduction of carbon–heteroatom double bonds is espe- (OD13). The resulting reduced eosin Y•− could then perform a
cially easy and leads to the formation of ketyl radical anions or reduction of the alkyne to generate a radical anionic species.
their equivalents with other heteroatoms. However, organopho- The latter would be subsequently protonated before recom-
tocatalysts have been only rarely used for this type of reduction. bining with the sulfonyl radical to afford the desired vinyl
sulfones.
C2-charged radical species
Since 2013, the Nicewicz group has developed a multitude of
methodologies for the anti-Markovnikov hydrofunctionaliza-
tion of alkenes, exploiting the reactivity of alkene radical
cations generated using organic dyes [96,97]. Their seminal
work reported the oxidation of the alkenols 22.1 by the
Fukuzumi dye (OD2, Scheme 22) [98]. The so-formed radical
cation undergoes an intramolecular nucleophilic 5/6/7-exo-trig-
cyclization to give the cyclic ethers 22.3. Mes-Acr-Me+ (OD2)
is a strong enough oxidant (E(PC+*/PC) ≈ 2.1 V), allowing the
oxidation of unactivated alkenes (1.2 ≤ Eox ≤ 1.9 V). In this
transformation, the cocatalyst 22.2 acts as an H atom shuttle.
This alkene radical cation-based strategy has been extended to Scheme 23: Illustrative example for the reductive photocatalytic gener-
various hydrofunctionalizations of styrenes with mineral acids ation of an alkene radical anion from alkynes: the Markovnikov-selec-
tive sulfonylation of alkynes reported by Lei and co-workers [100].
(hydrochloric acid, hydrofluoric acid, phosphoric acids, and
C–X radical anions and derived neutral radicals

Amidst charged radical species, ketyl radicals play a central role
in organic synthesis (Figure 3). As intermediates, they are more
stable because the charge is mainly localized on the oxygen
atom. They are postulated to be the intermediate of important
reactions, such as the pinacol [101] or the McMurry coupling
[102]. Recently, photocatalysis has been used to access ketyl
radicals through the reduction of ketones with a suitable transi-
tion metal-based photocatalyst [103] or organic dye [104]. The
protonation of this type of radicals occurs on the heteroatom
and leads to versatile neutral C(sp3) radicals. Such processes
Scheme 22: Illustrative example for the oxidative photocatalytic gener- can also occur via concerted proton-coupled electron transfer
ation of alkene radical cations from alkenes: the hydroetherification of mechanisms [105]. Similarly, the photocatalyzed reduction of
alkenes reported by Nicewicz and co-workers [98].
imines followed by protonation, as well as the reduction of
1174
iminium compounds, gives access to α-amino radicals [106]. various N-heterocycles 25.2 for the synthesis of the C–H func-
Most approaches are based on inorganic photocatalysts. As a tionalization products 25.3 with fine-tuned Mes-di(t-Bu)Acr+
rare example of the use of an organic dye, Dixon and (OD4) as a photocatalyst. In this transformation, the arene is
co-workers used eosin Y (OD13) to reduce imines and generate first oxidized by the excited state of the photocatalyst, gener-
the α-amino C(sp3) radical upon protonation (Scheme 24) [107]. ating the arene radical cation I. The latter then undergoes a
This radical is then trapped with a suitable Michael acceptor nucleophilic attack of the N-heterocycle, affording the radical
24.2 to obtain the corresponding allylation product 24.3 after a adduct II. TEMPO and O2 act as oxidants for the formation of
desulfonylation. the final aromatic compound via the peroxo radical III when
using O2. Nicewicz and co-workers noticed that the presence of
nucleophilic peroxide radicals generated from O2 led to the deg-
radation of the classical Mes-Acr+ photocatalyst. The presence
of bulky tert-butyl groups in the 3- and 6-positions provided a
greater catalyst stability in presence of such nucleophilic radi-
cals. This arene radical cation strategy has been further extend-
ed to cyanations, aminations, and fluorinations [111-116].
Figure 3: Structure of C–X radical anions and their neutral derivatives.
Scheme 24: Illustrative example for the photocatalytic reduction of

imines and the generation of an α-amino C(sp3) radical: the umpolung
of imines for allylations reported by Dixon and co-workers [107].
Enones can also be subject to SET reductions through Scheme 25: Illustrative example for the oxidative photocatalytic gener-
photoredox catalysis, and this can lead to [2 + 2] cycloadditions ation of aryl radical cations from arenes: the C–H amination of arenes
reported by Nicewicz and co-workers [110].
[2,108]. Similar intermediates can also be generated through the
direct activation of the ß-C–H bond [109]. However, organic
dyes have not yet been broadly applied for such transformat- Arene radical anions, resulting from the reduction of aromatic
ions. compounds, are transient species that can enable aryl radical
generations, in particular with haloarenes (see the section on
Charged aryl radical species aryl radicals from aryl halides). Notably, cyanobenzenes have
Arene radical cations are valuable intermediates that enable the been reported to undergo reductions and lead to ipso-substitu-
direct C–H functionalization of the aromatic species. They can tion in place of the cyano group [117]. However, these method-
be accessed through the oxidation of arenes under relatively ologies rely on either a transition metal photocatalyst [118,119]
strong oxidative conditions (Eox > +1.0 V). or the formation of EDA complexes (electron donor–acceptor
complexes) [120-123], and no method involving organophoto-
Following up their work on alkene oxidations, Nicewicz and catalysts has been reported yet to the best of our knowledge.
co-workers have developed several strategies for arene func-
tionalizations through arene radical cation intermediates. Their Nitrogen-centered radicals (NCRs)
work relies on the careful tuning of the Mes-Acr+ scaffold. In Biologically relevant compounds often contain C–N bonds,
2015, they developed a site-selective C–H amination of arenes rendering the development of efficient methodologies for their
(Scheme 25) [110]. The arenes 25.1 could be aminated by formation of paramount importance. Building on the seminal
1175
work of Zard [124], NCRs have emerged as key reactive inter- Iminyl radical generation
mediates. The reductive cleavage of weak N–X (X = halogen, Hydroxylamines have emerged as key precursors for iminyl
S, O) bonds using a stoichiometric initiator or high tempera- radical generation [128]. Their redox properties can be easily
tures set the path for key developments for the generations of tuned through the substitution pattern of the electrophore. They
NCRs, for instance, in the Hofmann–Löffler–Freytag reaction. can be subjected to either oxidative or reductive SET with an
With the rise of photoredox catalysis, they could be accessed excited photoredox catalyst. The most used scaffolds consist of
under milder conditions in the last years [125-132]. electron-poor O-acyl and O-aryl hydroxylamines, which are
prone to reduction, and α-N-oxy acids, which undergo oxida-
NCRs can be organized into four main classes depending on the tions followed by β-scission [128,136,139].
nitrogen atom hybridization and the substitution of the N atom,
including iminyl, amidyl, aminyl, and aminium units Leonori first described how O-aryl oximes 27.1 can be used to
(Scheme 26). The reactivity depends on the philicity of each efficiently generate an iminyl radical in the presence of eosin Y
species. In a general manner, NCRs are prone to the addition to (OD13, Scheme 27) [140]. This methodology was employed in
unsaturated systems, either inter- or intramolecularly as well as hydroimination and iminohydroxylation cyclization reactions
HAT and Norrish type I fragmentations. Each of these steps to give the pyrrolines 27.2. The transformation proceeds
generates a C-centered radical, later subject to termination. The via a SET reduction of the electron-poor aromatic moiety on the
variety of possible transformations has already been reviewed oxime to give a radical anion, which then fragments. Electro-
[125-132]. chemical studies highlighted that O-aryl hydroxylamines bear-
ing nitro groups were within the reduction range of excited
Iminyl radicals have an ambiphilic character. Amidyl radicals eosin Y (E red between −0.55 and −0.93 V vs SCE, OD13,
are electrophilic, with the substitution playing an important role E(PC •+ /PC*) ≈ −1.1 V).
[133-135]. As they are prone to efficient HAT, C(sp 3 )–H
couplings at remote positions have been intensively studied
[128,130,132,136]. Aminyl and aminium radicals display the
opposite philicity: aminyls are nucleophilic, whereas upon pro-
tonation, the generated aminium is strongly electrophilic.
N-Centred radical cations have been employed as key interme-
diates in amine syntheses [137,138]. These species can further
react, according to the structure of the substrate, to form either
iminium ions or C-centered radicals, such as α-amino radicals.
Several approaches for their efficient generation with organic

dyes have been proposed, using SET oxidations and oxidative
or reductive fragmentations. The hydroxylamine scaffold plays
a prevalent role in the generation of various NCRs, both Scheme 27: Illustrative example for the photocatalytic reductive gener-
through oxidative or reductive fragmentation. N-aminopyri- ation of iminyl radicals from O-aryl oximes: the hydroimination/cycliza-
tion reported by Leonori and co-workers [140].
dinium salts are also emerging starting materials.
Scheme 26: NCR classifications and generation.
1176
Oxidative strategies have also been described using the

hydroxylamine scaffold, affording an efficient and general
access to iminyl radicals. The first reports were released simul-
taneously by Leonori and Studer (Scheme 28) [141,142]. α-N-
Oxy acid 28.1 carboxylates (E ox = +1.6 V vs SCE for the
caesium carboxylate) can be oxidized by the strongly oxidizing
dye Mes-Acr-Me + (OD2, E(PC + */PC) ≈ 2.1 V). After the
decarboxylation and β-scission, the corresponding iminyl radi-
cals were submitted to various radical traps, Y-FG, to provide
diverse imino-functionalized products 28.2. A large variety of
functionalizations was possible, such as halogenations, azida-
tions, olefinations, or alkynylations. This activation mode was
employed by the same group in a cascade strategy, which Scheme 29: Illustrative example for the photocatalytic oxidative gener-
allowed a remote functionalization [143]. To extend the scope ation of iminyl radicals via an N–H bond oxidation: the radical cycliza-
tion reported by Li and co-workers [145].
of such transformations, our group reported novel organic dyes
in 2018, such as 4ClCzIPN (OD8), obtained through fine-tuning
of 4CzIPN (OD6), which are both strong oxidants and reduc- The generation of amidyl radicals using organophotoredox ca-
tants [144]. talysis was first reported by Pandey and Laha in 2015
(Scheme 30) [146]. They developed an intermolecular cross-
dehydrogenative benzylic C(sp3) amination between the aryl
substrates 30.1 and the amides 30.2 for the synthesis of the
Weinreb amides 30.3 using DCA (OD5) as an organic dye.
Under visible-light irradiation, the SET oxidation of 30.2 by the
excited state of DCA, followed by a deprotonation, afforded the
amidyl radical. This radical behaved as a powerful HAT
reagent, allowing the formation of the benzylic radical from
30.1. The absence of any activating group on the nitrogen
renders this process atom-economical.
Scheme 28: Illustrative example for the photocatalytic oxidative gener-

ation of iminyl radicals from α-N-oxy acids: the imino functionalization
reported by Leonori and co-workers [141].
In the search for a more atom-economical approach, the group

of Li developed an iminyl radical formation by the N−H bond
cleavage from the diarylimines 29.1 (Scheme 29) [145]. The
direct oxidation of 29.1 was achieved using Mes-Acr-Me +
(OD2) and a cobalt cocatalyst, ensuring an efficient dehydroge-
nation. Various N-heterocycles 29.3 were accessed via a radical Scheme 30: Illustrative example for the photocatalytic oxidative gener-
cyclization cascade with the alkyne derivatives 29.2. ation of amidyl radicals from Weinreb amides: the cross-dehydrogena-
tive benzylic C(sp3)–H amination reported by Pandey and Laha [146].
Amidyl radical generation

The oxidation of amides is more difficult compared to amines, In 2016, the Leonori group paved the way for the generation of
with reduction potentials from 1.2 to 2.0 V vs SCE [138]. This amidyl radicals by SET reductions of hydroxylamines
has rendered the development of a general strategy for direct (Scheme 31) [134]. The previously described approach for
amidyl radical formations challenging. A successful approach iminyl radical formations was employed [140]. The same
has been the incorporation of a photolabile moiety on the tunable aryloximes 31.1 were used as electrophores to generate
nitrogen atom. Similar to the iminyl radical generation, the use the desired amidyl radicals. This methodology allowed the de-
of hydroxylamine derivatives has turned out to be very efficient velopment of a hydroamination/cyclization cascade to give the
[128,139]. heterocycles 31.2 and intermolecular N-arylations. A modified
1177
electrophore, p-CF3-substituted hydroxamide, was later pro- centered radicals with various reagents. Studer and co-workers
posed by the Yu group with a different dye, (2,4,6-tri(9H- disclosed an amidofluorination of unactivated alkenes and the
carbazol-9-yl)-5-chloroisophthalonitrile (3CzClIPN) [147]. styrenes 33.1 to give the fluorinated amides 33.3, employing the
α-amido-oxy acids 33.2 and Mes-Acr-Me+ (OD2, Scheme 33)
[149]. The same electrophore allowed a remote functionaliza-
tion of amides to take place, as disclosed by the Leonori group
[135]. 4CzIPN (OD6) was reported to be a suitable dye for the
SET oxidation of such carboxylates.

ation of amidyl radicals from hydroxylamines: the hydroamination/cycli-
zation reported by Leonori and co-workers [134].
The N-aminopyridinium salts 32.2 are another scaffold for the Scheme 33: Illustrative example for the photocatalytic oxidative gener-
generation of amidyl radicals via SET. After the reduction, a ation of amidyl radicals from α-amido-oxy acids: the amidofluorination
of unactivated alkenes reported by Studer and co-workers [149].
fragmentation affords the desired amidyl radicals together with
the corresponding pyridines. The reduction potential of such
species was around −0.75 V vs Ag/Ag+, depending on the sub- Aminyl and aminium radical generation
stitution pattern. This scaffold was employed recently by the The prevalent strategy for accessing aminium radicals is SET
Hong group to achieve an intermolecular alkene 1,2-aminopy- oxidations. The efficiency of this approach is closely related to
ridylation to give the difunctionalized products 32.3 the stabilization of the generated radical on the substrate (delo-
(Scheme 32) [148]. Eosin Y (OD13) was an efficient dye for calization, electronic effects) or through a strain release ring-
the SET reduction of the N-aminopyridinium salts, which act as opening driving force.
bifunctional reagents as the released pyridine later added to the
olefin 32.1. N-Aryltetrahydroquinolines 34.1 have been intensively studied
as a privileged scaffold for N-centred radical cation formations
[138]. After iminium formation, formed by subsequent HAT on
the amine radical cation, various nucleophiles can add, result-
ing in diverse functionalizations. In 2011, König and
co-workers [150] demonstrated that eosin Y (OD13) was an
efficient dye for an aza-Henry reaction [151], affording the
tetrahydroquinolines 34.2 (Scheme 34). Simultaneously, the
Tan group described the use of rose bengal (OD15) in the same
transformation [152].
Regarding the strain release approach, the Xiao group reported

a synthesis of the pyrroles 35.3 in 2014 [153]. They can be
ation of amidyl radicals from N-aminopyridinium salts: the intermolecu- accessed via a photocatalytic formal [3 + 2] cycloaddition of the
lar alkene 1,2-aminopyridylation reported by Hong and co-workers 2H-azirines 35.1 and the alkynes 35.2 (Scheme 35). The use of
[148].
Mes-Acr-Me+ (OD2) was successful due to its high reduction
potential in the excited state, together with an intense absorp-
The generation of amidyl radicals by the SET oxidation of tion in the visible-light region. The transformation proceeds via
hydroxylamines has also been explored. As for iminyl radicals, the single-electron oxidation of 2H-azirines, forming a nitrogen-
this enables the trapping of the subsequently formed carbon- centered radical cation, which is prone to ring opening.
1178

ation of aminium radicals: the N-aryltetrahydroisoquinoline functionali-
zation reported by König and co-workers [150]. Scheme 36: Illustrative example for the photocatalytic oxidative gener-
ation of nitrogen-centered radical cations from cyclopropylanilines: the
[3 + 2] annulation of cyclopropylanilines and cyclopropenes reported
by our group [154].

ation of nitrogen-centered radical cations from 2H-azirines: the pyrrole
synthesis reported by Xiao and co-workers [153].
ation of hydrazonyl radical from hydrazones: the pyrazoline synthesis
reported by Xiao and co-workers [156].
The driving force of the ring strain release and irreversible ring
opening of nitrogen-containing small rings was also exploited
by our group in 2019 (Scheme 36) [154]. Starting from the The pyrazolines 37.2 are formed through an intramolecular ad-
aminocyclopropanes 36.1 and the cyclopropenes 36.2, a [3 + 2] dition to the alkene, followed by a reaction with oxygen.
annulation led to the bicyclo[3.1.0]hexanes 36.3. Under visible-
light irradiation, the excited-state photocatalyst OD7 performs Finally, a remote functionalization of protected amines was also
an SET oxidation of an cyclopropylaniline 36.1, leading to an disclosed by Leonori and co-workers in their report on amidyl
N-centred radical cation after ring opening. The latter under- radical formations by SET oxidations of α-oxyamido acids
goes a [3 + 2] annulation with cyclopropenes 36.2, affording a using 4CzIPN (OD6, Scheme 28) [135].
bicyclic product 36.3. The key to the broad substrate tolerance
relied on using 4DPAIPN (OD7), which is a mild oxidant but a Oxygen-centered radicals
strong reductant (E(PC*/PC •− ) = +0.90 and E(PC/PC •− ) = Oxygen-centered radicals (O-radicals) represent an important
−1.65 V vs SCE) [155]. class of heteroatom-centered radicals. In particular, their ability
to promote radical translocations, especially HATs, and to
As another class of nitrogen radicals, hydrazonyl radicals can be undergo β-fragmentations makes them valuable reactive inter-
formed from the direct N–H bond oxidation of the hydrazones mediates in organic synthesis [157-161]. Organic photoredox
37.1, as reported by the Xiao group (Scheme 37) [156]. This catalysis can be exploited to access O-radicals from different
strategy was based on a cooperative TEMPO and photoredox classes of substrates. In particular, N-alkoxypyridinium and
catalysis. The SET oxidation of the anion of the β,γ-unsaturated alkyl hydroperoxides have been exploited as competent
hydrazones 37.1 is mediated by TEMPO+, itself formed by an O-radical sources (Scheme 38). These substrates can be acti-
SET oxidation with the excited state of Mes-Acr-Me+ (OD2). vated through SET reduction and energy transfer, respectively.
1179
perform a ring closure/pyridylation radical cascade for the syn-

thesis of tetrahydrofuran derivatives (Scheme 39b) [161].
Eosin Y (OD13) has been demonstrated to be another compe-

tent photocatalyst for the generation of O-centered radicals from
N-alkoxypyridynium salts. These radicals have been used as
initators for the synthesis of highly functionalized
benzo[b]phosphole oxides from arylphosphine oxide and
alkynes [162].
Scheme 38: Generation of O-radicals.
Alkyl hydroperoxides can act as oxidants in photocatalytic

The cleavage of the N–O or O–O bond releases the desired cycles, furnishing the desired alkoxy radicals. Several organic
O-radical. dyes have been exploited in these processes, including eosin Y
(OD13) [163] and acridine red [164]. Wang and co-workers
The ability of N-alkoxypyridinium salts to generate O-radicals relied on this approach for the development of an organophoto-
under organophotocatalytic conditions was exploited by Hong, catalytic vinylation of tetrahydrofuran derivatives with alkynes
Baik, and co-workers (Scheme 39a) [160]. They reported the (Scheme 40) [165]. In this method, the photoexcited OD13 in-
use of the phosphorylated quinolinone derivative OD21 as a duces the cleavage of the weak O–O bond of tert-butyl peroxide
photocatalyst, which triggers the photoinduced SET reduction (40.1), generating a hydroxy radical and a tert-butoxy radical.
of the N-alkoxypyridinium salt 39.1, leading to the formation of The latter promotes an H abstraction from the substrate tetra-
the key O-radical. This species rapidly undergoes a 1,5-HAT. hydrofuran (8.1), giving access to an α-oxy C(sp 3 ) radical,
The formed nucleophilic C-centered radical then adds selec- which is trapped by an alkyne 40.2, providing the desired vinyl-
tively onto the C4 position of another pyridinium substrate 39.1. ation product 40.3.
The formed N-alkoxylated intermediate is converted into the
desired product 39.2 after oxidation and releases another alkoxy
radical at the same time. The measured quantum yield (Φ = 4.4)
indicates that a chain mechanism is operative. Recently, the
same group applied a similar organophotocatalytic system to
Scheme 40: Illustrative examples for the photocatalytic generation of

O-radicals from alkyl hydroperoxides: the vinylation of tetrahydro-
furans reported by Wang and co-workers [165].
Sulfur-centered radicals
Thiyl (sulfenyl) radicals
Thiyl radicals are common, versatile, strong nucleophilic radi-
cals. They are efficient at performing atom abstractions, in par-
ticular with H-atoms, adding to π-systems and electrophiles,
such as carbonyl compounds [166]. They can be generated from
the UV irradiation of disulfides, sulfides or even thiols [167].
However, their use in organophotocatalysis is scarce. In substoi-
chiometric quantities, they are efficient H atom shuttles and
play a primordial role in hydrogen transfer mechanisms. For
Scheme 39: Illustrative examples for the photocatalytic generation of this reason, one of their major applications is the HAT to the
O-radicals from N-alkoxypyridinium salts reported by Hong, Baik and cocatalyst (Scheme 3 and Scheme 9) [41,60]. In stoichiometric
co-workers [160,161].
amounts, they generally add efficiently to π-systems and can be
1180
applied in thiol-ene reactions. Recently, Dilman and co-workers The fragmentation of sulfonyl chloride derivatives requires rela-
published a hydrosulfenylation of the β-difluorostyrenes 41.2 tively strong reductive conditions. Most reductions occur at
for the synthesis of the thioethers 41.3 using 9-PhAcr (OD1) as −1.30 V or lower values (with the exception of CF 3 SO 2 Cl:
a photocatalyst (Scheme 41) [168]. The formed thioethers 41.3 Ered = –0.18 V). Organophotocatalysis has been exploited to
could then be used as a gem-difluoroalkyl radical source for promote this reduction. For example, Chen and co-workers de-
further transformations. Interestingly, 9-PhAcr (OD1) can only signed the new organic dye OD17 in 2018 (Scheme 43,
act as a photocatalyst in its protonated form. The thiol 41.1 acts E(PC•+/PC*) ≈ −1.9 V), able of reducing the arylsulfonyl chlo-
as a proton source for OD1, allowing it to undergo a photoexci- rides 43.1 (Ered = −0.94 V) to initiate the synthesis of the poly-
tation, leading to the excited state that can then oxidize the thio- acrylates and polyacrylamides 43.3 [173].
late and generate the key S-centered radical. The latter then
adds to the styrene. Other reports describe the use of phenyl
glyoxylic acid [169] or eosin Y (OD13) for thiol-ene [170] and
thiol-yne reactions [171].
Scheme 43: Illustrative example for the reductive photocatalytic gener-

ation of sulfonyl radicals from arylsulfonyl chlorides: the acrylate and
acrylamide polymerization reported by Chen and co-workers [173].
Scheme 41: Illustrative example for the oxidative photocatalytic gener- To bypass the strong reductive conditions communally used for
ation of thiyl radicals from thiols: the thiol-ene reaction with β-difluo- the activation of sulfamoyl chlorides to form the corresponding
rostyrenes reported by Dilman and co-workers [168].
sulfamoyl radicals, Gouverneur and co-workers developed an
efficient method based on chloride abstractions. They could
Sulfonyl radicals successfully convert the sulfamoyl chlorides 44.1 to the alkyl
Sulfonyl radicals show a good reactivity with π-systems, sulfonamides 44.4 using eosin Y (OD13) as a photocatalyst and
allowing the synthesis of nonsymmetrical sulfones [172]. How- the supersilane 44.3 for a halogen abstraction (Scheme 44)
ever, they are also prone to fragmentations, resulting in the [174]. Under visible-light irradiation, the excited state OD13*
desulfonylation of the substrate and the generation of the corre- can oxidize the silane, generating, after deprotonation, a silyl
sponding C-centered radical. Sulfonyl radicals can be obtained radical, which can efficiently abstract the chlorine atom, result-
from the fragmentation of sulfonic acid analogues, such as sul- ing in the nucleophilic sulfamoyl radical. The latter can then
fonyl chlorides or sulfonyl hydrazides under reductive or oxida-
tive conditions. Sulfinic acids can also be readily oxidized in
the presence of a base, affording the desired sulfonyl radical
(Scheme 42).
Scheme 44: Illustrative example of a Cl atom abstraction strategy for

the photocatalytic generation of sulfamoyl radicals from sulfamoyl chlo-
Scheme 42: Main strategies and reagents for the generation of sulfo- rides: the radical chlorine abstraction for a Giese reaction reported by
nyl radicals used in organophotocatalysis. Gouverneur and co-workers [174].
1181
undergo a Giese addition to an electron-deficient alkene 44.2, Additionally, energy sensitization has emerged has a powerful
affording the desired alkyl sulfonamides 44.4. strategy for promoting the contrathermodynamic E-to-Z isomer-
ization of olefins. Inspired by the mechanism of vision in
The SET oxidation of sulfinic acids and sulfinates for the gener- mammals, which implies a triplet state-mediated E-to-Z isomer-
ation of sulfonyl radicals has been thoroughly explored over the ization of retinal, Gilmour and co-workers reported an
past decades [172]. These oxidations occur under mildly oxida- organophotocatalytic method for the isomerization of the α,β-
tive conditions, and eosin Y (OD13) stands out as an efficient unsaturated esters 46.1 (Scheme 46) [180]. In this protocol,
photocatalyst for these steps [175-177]. This strategy is also (−)-riboflavin (OD11) is exploited as an organic photocatalyst,
compatible with transition metal catalysis, as shown by Lei and capable of absorbing light, transferring its triplet energy to the
co-workers with an organophotocatalyzed radical cross-cou- E-substrate and triggering the isomerization of the double bond
pling method using the aryl sulfinic acids 45.1 and the styrenes with a high level of selectivity.
45.2 to generate the allyl sulfones 45.3 (Scheme 45) [178].
Under visible-light irradiation, the aryl sulfinic acid 45.1 is
oxidized by the excited-state photocatalyst, a bis(tetrabutylam-
monium) salt of eosin Y, OD23, generating the desired sulfo-
nyl radical. The latter adds to the styrene 45.2, and the formed
benzylic radical is intercepted by the cobalt catalyst, which can
promote a dehydrogenation to form the allyl sulfone 45.3. The
colbalt cocatalyst secures the turnover of the photocatalyst by
reducing it back to its ground state.
Scheme 46: Illustrative example for the photocatalytic generation of

electronically excited triplet states: the E-to-Z isomerization of olefins
reported by Gilmour and co-workers [180].
Recently, the same group extended this strategy to the geomet-

rical isomerization of several classes of substrates, including
β-ionyl derivatives [181], alkenylsilanes [182], and vinyl phos-
phonates [183]. In addition to riboflavin, other organic dyes,
such as benzophenone, anthracene, 2-iodo-9-fluorenone [184],
Scheme 45: Illustrative example for the oxidative photocatalytic gener- and carbazole- and cyanobenzene-based organophotocatalysts
ation of sulfonyl radicals from sulfinic acids: the metallaphotoredox allyl [185] have been successfully employed as photosensitizers for
sulfone synthesis reported by Lei and co-workers [178].
these isomerizations.
Excited reactive intermediates (energy Another application of photosensitization is related to the devel-
transfer) opment of thermally forbidden [2 + 2] cycloadditions. These
In addition to electron transfer and atom transfer, EnT is one of reactions can be promoted by the direct excitation of the sub-
the key modes of activation employed in photocatalysis. In strate, generally using UV light. However, the key triplet state
order to act as a good energy transfer catalyst, an organic mole- intermediate can also be accessed by the energy transfer from a
cule, upon light irradiation, should undergo a productive inter- suitable photosensitizer. Seminal reports by Bach [186] and
system crossing (ISC) and reach an electronically excited triplet Sivaguru [187] demonstrated that thioxanthone-based organic
state. The latter can transfer its energy to a ground-state sub- dyes can promote these transformations. It has been shown that
strate in a process named “sensitization”. The so-formed excited flavin-based dyes can also act as photosensitizers for this reac-
substrate is a valuable reactive intermediate for achieving tion (Scheme 47) [188]. In particular, alloxazine (OD12), which
various transformations and structural modifications. This ap- is structurally similar to flavin, has been used for promoting an
proach has been widely exploited to generate singlet O 2 , a intramolecular [2 + 2] cycloaddition of the dienes 47.1 to form
versatile oxidant often applied in organic synthesis [179]. the cyclobutane 47.2.
1182
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Photocatalysis with organic dyes: facile access to reactive

intermediates for synthesis

Review Open Access

Address: Beilstein J. Org. Chem. 2020, 16, 1163–1187.

Keywords: Guest Editor: T. Noël

Scheme 1: Activation modes in photocatalysis.

For example, Nicewicz developed a photocatalytic hydrodecar-

Scheme 2: Main strategies for the formation of C(sp3) radicals used in

König reported a visible light-promoted photochemical reduc-

The organic dye 4CzIPN (OD6), due to its oxidative abilities in

(hetero)arene product 5.3 is obtained after the reductive elimi-

Scheme 6: Illustrative example for the photocatalytic oxidative genera-

Other reductive fragmentations

Scheme 5: Illustrative example for the photocatalytic oxidative genera-

Finally, the same group developed a photochemical radical

For an example of the first strategy, Zhang and co-workers de-

Scheme 12: Illustrative examples for the photocatalytic reductive gen-

2014 [81]. As depicted in Scheme 13 (box 1), the conPET

that rose bengal (OD15) acts as an energy transfer sensitizer

Scheme 15: Illustrative example for the reductive photocatalytic gener-

Scheme 17: Illustrative example for the decarboxylative photocatalytic

Scheme 16: Main strategies towards acyl radicals used in organopho-

Scheme 20: Illustrative example of the photocatalytic HAT approach

Alkenyl and aryl radical ions (radical cations

C–X radical anions and derived neutral radicals

Scheme 24: Illustrative example for the photocatalytic reduction of

Several approaches for their efficient generation with organic

Scheme 26: NCR classifications and generation.

Oxidative strategies have also been described using the

Scheme 28: Illustrative example for the photocatalytic oxidative gener-

In the search for a more atom-economical approach, the group

Amidyl radical generation

Scheme 31: Illustrative example for the photocatalytic reductive gener-

Regarding the strain release approach, the Xiao group reported

Scheme 34: Illustrative example for the photocatalytic oxidative gener-

Scheme 35: Illustrative example for the photocatalytic oxidative gener-

perform a ring closure/pyridylation radical cascade for the syn-

Eosin Y (OD13) has been demonstrated to be another compe-

Alkyl hydroperoxides can act as oxidants in photocatalytic

Scheme 40: Illustrative examples for the photocatalytic generation of

Scheme 43: Illustrative example for the reductive photocatalytic gener-

Scheme 44: Illustrative example of a Cl atom abstraction strategy for

Scheme 46: Illustrative example for the photocatalytic generation of

Recently, the same group extended this strategy to the geomet-

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The definitive version of this article is the electronic one

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