10 1021@acscatal 0c03418

pubs.acs.
org/acscatalysis Perspective
Direct Synthesis of Multi(boronate) Esters from Alkenes and Alkynes

via Hydroboration and Boration Reactions
Xianjin Wang, Yue Wang, Wei Huang, Chungu Xia,* and Lipeng Wu*
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ABSTRACT: Multi(boronate) esters have been attracting increasing attention as

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versatile building blocks for the succinct and precise synthesis of complex molecules.
However, there are a limited number of efficient synthetic procedures available. In this
respect, the direct multiboration of alkenes and alkynes is undoubtedly an ideal route
for their synthesis. During the past 30 years, catalytic systems based on transition-
metals, organophosphines, bases, and even catalyst-free systems, with heat or with light
irradiation for their straightforward preparation from alkenes and alkynes have been developed. Multi(boronate) esters with different
numbers (up to 4) and positional relationships of the adjacent boron moieties were obtained, which are summarized and discussed
herein.
KEYWORDS: boronate esters, alkenes, alkynes, hydroboration, boration
1. INTRODUCTION manner, which allows the production of a large range of

Organoboronates are synthetically valuable compounds used complex molecules for the synthesis of drugs, natural products,
for a wide range of transformations due to their versatile and functional materials.6 As one example, their applications in
reactivity, relative stability, and high functional group the synthesis of materials with aggregation-induced emission
compatibility.1 Boron-containing molecules also play impor- (AIE) properties for potential utilization in biological imaging
tant roles in medicinal and materials chemistry.2 In this and chemical sensing has been demonstrated.7 Furthermore,
respect, multi(boronate) esters are emerging as valuable multi(boronate) esters have been investigated in vitro as
reagents.3 The reactivities of multi(boronate) esters are potential matrix metalloproteinase (MMP-2) inhibitors, as
tunable and largely dependent on the positional relationship illustrated by vinyl tris(boronate) ester 4 at 5 μM.8
of neighboring boron moieties. Take gem-bis(boronate) esters, Despite their high synthetic value and wide range of
for example; the boron moiety can stabilize adjacent potential applications, there is a limited number of efficient and
carbanions and thereby facilitate base-promoted deboration atom-economical procedures available for the preparation of
to produce the reactive α-boryl carbanions 1.4 When a bulkier multi(boronate) esters.9 Traditionally, they were synthesized
and stronger base such as lithium 2,2,6,6-tetramethylpiperidine from organic halides, which typically generate stoichiometric
(LiTMP) is used, deprotonation takes place to produce gem- amounts of salts, require a large quantity of strong base, and
bis(boryl) carbanions 2 (Scheme 1).5 On the other hand, have narrow substrate and poor functionaly tolerance. On the
internal chelation is proposed to enhance the Lewis acidity of other hand, alkenes and alkynes, which could be obtained from
vic-bis(boronate) esters in 3 and enable efficient cross-coupling the petroleum industry or renewable sources,10 are abundant
reactions. Therefore, boron moieties within one molecule can and inexpensive feedstocks. Several straightforward methods
be differentiated and transformed in a selective and stepwise are also available on the laboratory scale for alkene and alkyne
preparation with complex molecule structures for fine chemical
Scheme 1. Distinctive and Diverse Synthetic Application of purposes. Thus, an efficient, selective, and practical multi-
Multi(boronate) Esters boration of alkenes and alkynes has become a major focus in
organic chemistry over the past few decades. This Perspective
will describe the development of and recent advances in the
Received: August 5, 2020

Revised: November 23, 2020
© XXXX American Chemical Society https://dx.doi.org/10.1021/acscatal.0c03418

1 ACS Catal. 2021, 11, 1−18
ACS Catalysis pubs.acs.org/acscatalysis Perspective
direct (catalytic or stoichiometric) synthesis of multi- Scheme 2. Transition-Metal-Catalyzed 1,1-Diboration of

(boronate) esters from alkenes and alkynes using either Alkynes
borane or diboron as the boration regent via hydroboration or
boration reactions. The text is divided into sections based on
the types of different multi(boronate) esters, and in each, their
preparation from alkynes, alkenes, or borylalkenes are
classified. It is noted that in 1998 an early review on the
transition-metal-catalyzed diboration of unsaturated hydro-
carbons was published by Marder.11 In 2012, a review by
Iwasawa described the synthesis of bis(boronate) esters from
unsaturated hydrocarbons, with particular focus on vicinal
bis(boronate) esters.3a Much work has since been done in the
area of the trans-vicinal diboration of alkynes, geminal
diboration of alkynes and alkenes, and chain-walking/geminal
diboration of internal alkenes. In addition, interest in the direct
synthesis of tris(boronate) esters and tetra(boronate) esters
has almost only emerged over the past 5 years. Moreover,
excellent review contributions from Fernández, Masarwa, and
Wang focusing on the synthesis of one specific type of
multi(boronate) esters such as 1,1-diborylalkanes,3b,c,12 1,1-
diborylalkenes,13 or 1,1,2-triborylalkenes,14 have appeared in
the last 3 years, which indicated the emerging importance of
this field. In light of these significant achievements and the
importance of this research area, we, therefore, considered it
timely and pertinent to bring together these advances in the regioselective sequential hydroboration of alkynes to 1,1-
form of a Perspective focusing on the preparation of all types of diborylalkanes using an Rh(I) complex (Scheme 2b).22 Later
multi(boronate) esters from readily available alkenes and on, Yun using a CuCl/Xantphos/tBuOM (M = Li, Na) system
alkynes. The Perspective described here can be considered as achieved the first Cu-catalyzed 1,1-diboration of alkynes such
complementary material to the reviews of Marder, Iwasawa, as propargyl amide. It is worth noting that the deoxygenative
Fernández, Wang, and others dealing with related hydro- hydroboration of the amide functional group was not
boration and boration reactions.1e,15 observed.23 Then, Huang and co-workers applied cobalt
complex 7 to achieve a general alkyne 1,1-diboration process
2. gem-BIS(BORONATE) ESTERS (Scheme 2b).24 It is noted that the aforementioned systems
gem-Bis(boronate) esters have emerged as versatile building only worked for terminal alkynes, while the geminal diboration
blocks and fundamental intermediates for organic synthesis. of internal alkynes seems to be more challenging due to the
They can undergo either deprotonation5 or deboration4,16 for increased steric hindrance. Interestingly, Tsukada found that
further transformation simply in the presence of a base. the combination of CuBr with Phen or nBu3P could catalyze
Stereoselective desymmetrization of gem-bis(boronate) esters the geminal diboration of internal alkynes (Scheme 2c).25
was also realized via nucleophilic trifluorination.17 Further- However, the use of a diboron reagent and activated alkynes
more, cross-couplings such as arylation/alkylation,18 vinyl- leaves room for further exploration.
ations,19 and additions to epoxide20 or CX (X = N, O)- 2.1.2. Transition-Metal-Free 1,1-Diboration of Alkynes. It
containing compounds2e,21 demonstrate their fundamental has been reported that alkynes activated by an amide or ester
synthetic applications. However, the direct preparation of group reacting with a diboron reagent could give gem-
gem-bis(boronate) esters from bulk alkenes and alkynes has bis(boronate) esters simply using a base. Song and co-workers
only been developed in the past decade. Indeed, their found that ethyl propiolate reacting with B2pin2 in the presence
preparation from alkenes only appeared after 2017. This of 0.3 equiv. of K2CO3 and 10 equiv. of methanol could
might be because the traditional alkene hydroboration process selectively produce 1,1-diborylalkanes (Scheme 3). Mecha-
preferably produces the saturated monohydroborated prod- nistic studies supported a domino boration−protodeborona-
ucts, which terminate the reaction for further transformation, tion (DBP) process where the alkyne first reacted with B2pin2
while the direct diboration of alkenes normally produced vic- to render the vinyl boronate ester, which further diboronated
bis(boronate) esters. to produce 1,1,2-trisborylalkane 8. The latter was thought to
2.1. Synthesis of gem-Bis(boronate) Esters from be unstable under the basic conditions and underwent selective
Alkynes. 2.1.1. Transition-Metal-Catalyzed 1,1-Diboration protodeboration to produce 1,1-diborylalkanes.26
of Alkynes. Transition-metal-catalyzed hydroboration of
alkynes gives vinyl boronate esters (VBEs), the subsequent Scheme 3. K2CO3-Promoted 1,1-Diboration of Alkynes
hydroboration of which can produce 1,1-diborylalkanes.
However, the first hydroboration can produce linear and
branched VBEs, and the second hydroboration of VBE can
produce both geminal and vicinal bis(boronate) esters due to
the competing formation of intermediates 5 and 6 (Scheme
2a).22 Thus, three different bis(boronate) esters are possibly
produced together with other side reactions. This may be why
it was only until 2009 that Endo and Shibata achieved the first
2 https://dx.doi.org/10.1021/acscatal.0c03418
ACS Catal. 2021, 11, 1−18
In 2020, the Thomas group reported the use of 9- Scheme 5. Catalytic Dehydrogenative 1,1-Diboration of
borabicyclo[3.3.1]nonane (9-BBN) as a catalyst for the double Terminal Alkynes
hydroboration of alkynes. Mechanistic studies revealed a key
boron−boron exchange pathway: first, alkyne hydroboration
with 9-BBN produces (E)-alkenyl-B-9-BBN 9, then C(sp2)−
B/B−H transboration generated the (E)-alkenyl boronic ester
10, which underwent a second hydroboration with 9-BBN to
produce the mixed gem-diboryl intermediate 11. A final step of
C(sp3)−B/B−H transboration gave the gem-bis(boronate)
ester and regenerated 9-BBN (Scheme 4).27 It was noted that
the mixed intermediate 11 could be formed at room
temperature on a large scale with a stoichiometric amount of
9-BBN and an excess amount of HBpin.
Scheme 4. Synthesis of 1,1-Diborylalkanes from Alkynes via

Boron−Boron Transboration
From the aforementioned examples, we can see that

transition-metal complexes such as those of Rh, Co, and Cu
were able to catalyze the sequential 1,1-diboration of alkynes.
Normally the regioselectivity to 1,1-diboraiton was not an
issue; indeed, the coformation of vinyl boronate ester and a
saturated boronate ester was the main side reaction. Though
transition-metal-free systems have been developed, higher synthesis of 1,1-diborylalkene. After the formation of zinc
reaction temperature and catalyst loading were required in acetylide 19, C−Zn and B−H bond metathesis took place to
comparison to transition-metal catalysis, which normally form 20, which underwent subsequent hydroboration via a
causes selectivity issues. hydrozincation pathway to produce 1,1-diborylalkenes
2.2. Unsaturated gem-Bis(boronate) Esters. 2.2.1. Tran- (Scheme 5b).29
sition-Metal-Catalyzed 1,1-Diboration of Alkynes to 1,1- 2.2.2. Transition-Metal-Free Synthesis of 1,1-Diborylal-
Diborylalkene. The transition-metal-catalyzed 1,1-diborylalkene from Alkynes. The direct preparation of 1,1-dibor-
kene synthesis from alkynes normally underwent a first ylalkenes from activated alkynes such as propiolates,
deprotonation of a terminal alkyne to form a metal acetylide propiolamides, and 2-ethynylazoles using B2pin2 as the
intermediate, which after hydroboration or protoboration gave boration reagent was achieved by Sawamura and Ohmiya
1,1-diborylalkenes. Chirik and co-workers reported the use of and recently by Marder’s group simply using tBuOLi as the
cobalt complex 12 for the direct synthesis of 1,1-diborylalkenes catalyst. Like the transition-metal-catalyzed process, the
using B2pin2 or pinB-Bdan (dan = 1,8-diaminonaphthalene) as reaction was also commenced by the deprotonation of terminal
the boration reagent. It was proposed that, after the formation alkyne 21 with tBuOLi to form acetylide 22, which then
of the cobalt acetylide 13, diboron oxidative addition to 13 reacted with diboron to give alkynyl borate intermediate 23.
took place and formed 14, which underwent reductive Migration of the terminal boryl group in 23 to the C(sp) atom
elimination to produce the alkynylboronate complex 15. of the alkyne moiety generated allenoate intermediate 24,
Regioselective syn-cobaltation formed the vinyl cobalt which underwent proton transfer with tBuOH to form the 1,1-
intermediate 16, which then reacted with another alkyne to diborylalkene 25 (Scheme 6).30
produce 1,1-diborylalkenes (Scheme 5a).28 Using HBpin, From the reactions discussed above, we can see that, even
Ingleson and co-workers successfully applied NHC-Zn-H 18 though the transition-metal-free system was developed for the
(NHC = N-heterocyclic carbene) as the active catalyst for the synthesis of 1,1-diborylalkenes from alkynes, it requires
ACS Catal. 2021, 11, 1−18
Scheme 6. tBuOLi-Catalyzed Diboration of Electron- approach for the synthesis of 1,1-diborylalkanes from phenyl-,
Deficient Alkynes alkyl-. and cyclohexyl-substituted borylalkenes using dtbm-
Segphos or Josiphos as the ligand with HBpin (Scheme 8a).33
This copper system is a rare example in which diboron and
borane reagents give the same product. Apart from copper,
(PPh3)3CoH(N2) was also reported to mediate the hydro-
boration of alkyl borylalkenes to 1,1-diborylalkanes. Moreover,
the Co−H species was found to be a good double-bond
isomerization catalyst, which could mediate the 1,1-dibor-
ylalkane production from 27 (Scheme 8b). The boryl group on
27 was believed to have a directing effect for double-bond
isomerization.34
2.4. Synthesis of gem-Bis(boronate) Esters from
Alkenes. Alkenes are abundant and inexpensive feedstocks;
thus, the direct synthesis of 1,1-diborylalkanes from alkenes is
appealing. However, traditional alkene hydroboration with a
borane preferentially affords saturated monoborated prod-
ucts.35 Thus, a diboron reagent was first used in such
activated alkynes and only works with a diboron reagent. In transformations by Fu and Xiao with Ni(COD)2/Cy-XantPhos
addition, under transition-metal-free conditions, addition of a in the presence of MeOLi/Et3N, the application of which
proton source such as MeOH could shift the product from a allowed a large variety of terminal alkenes to be converted into
1,1-diborylalkene to a 1,1-diborylalkane. 1,1-diborylalkanes (Scheme 9).36
2.2.3. 1,1-Diborylalkene Synthesis from Vinyl Sulfide.
Niwa and Hosoya found that the reaction between 2-aryl vinyl
Scheme 9. Nickel-Catalyzed Synthesis of 1,1-Diborylalkanes
sulfides and B2pin2 catalyzed by rhodium gave an unexpected
from Alkenes
desulfanylative diboration product. Mechanistic studies dis-
closed that the formation of a vinyl boronate ester via syn
elimination of methylthiorhodium(I) complex 26 was the key
step (Scheme 7).31
Scheme 7. Rh-Catalyzed Synthesis of 1,1-Diborylalkene

from Vinyl Sulfide
To overcome the high reducing ability of borane for
selective 1,1-diborylalkane production, a catalyst should have a
balance of self-contradictory dehydrogenative boration and
hydroboration reactivities.35,37 Thus, to promote the dehydro-
genative boration of alkenes, Ge and co-workers introduced
another alkene as an H2 acceptor with Co(acac)2/Xantphos as
the catalyst to achieve the first 1,1-diboration of 1,1-
disubstituted alkenes with borane.38 Soon afterward, using
2.3. Synthesis of gem-Bis(boronate) Esters from (R)-DM-Segphos as the chiral ligand, they realized the
Borylalkenes. Hall and co-workers reported the first synthesis asymmetric 1,1-diboration of alkenes (Scheme 10a). Detailed
of optically pure 1,1-diborylalkanes from borylalkenes and mechanistic studies revealed that the reaction was initiated by
B2pin2 with CuCl in the presence of Walphos ligand (Scheme Co-H, which was converted into a Co-Bpin species during the
8a).32 Soon after, Yun and co-workers reported a more general hydrogenation of norbornene. Insertion of the alkene into the
Co-Bpin then formed the sterically hindered alkyl cobalt
Scheme 8. Copper- and Cobalt-Catalyzed Hydroboration of intermediate 28, which underwent valence tautomerization to
Borylalkenes the less hindered alkyl cobalt intermediate 29 via a cyclic σ,π
transition state.39 The alkyl cobalt intermediate 29 reacted
with HBpin to give 1,1-diborylalkanes and regenerate Co-H
species.40 Very recently, they also extended this system to the
synthesis of 1,1-diborylalkane from dienes. It is noted that, for
dienes, there is no need for dehydrogenative boration ability;
thus, no additional alkenes were required. However, the
selective production of 1,1-diborylalkane from dienes was
challenging in terms of regio- and chemoselectivities, as several
possible isomers could be produced. A boryl-directed chain-
walking hydroboration of alkenyl boronate esters that were
generated from anti-Markovnikov 1,2-hydroboration of 1,n-
diene was proposed to account for the regioselectivity (Scheme
10b).41
Apart from nickel and cobalt, early transition-metals have
also been applied in the 1,1-diboration of alkenes and showed
ACS Catal. 2021, 11, 1−18
Scheme 10. Cobalt/Phosphine System for the Synthesis of and stricter regioselectivity demanded of the former. In all of
1,1-Diborylalkanes from Alkenes the reported systems, a 1,1-diborylalkene was found to be a key
intermediate to 1,1,1-tris(boronate) esters. For example, in
their use of cobalt complex 12 catalyzed diboration of alkynes
to 1,1-diborylalkenes, Chirik added the terpyridine cobalt
complex 30 to mediate the further hydroboration of in situ
generated 1,1-diborylalkenes, and 75% of the corresponding
1,1,1-triborylalkane was obtained (Scheme 12a).28 The
Scheme 12. One-Pot Two-Step Synthesis of 1,1,1-

Triborylalkanes from Alkynes
strategy of combining two catalysts for the synthesis of 1,1,1-

triborylalkanes demonstrated the inherent difficulty of such a
transformation, which requires dehydrogenative boration and
hydroboration activity in a system. This strategy was also used
by Ingleson, who added 10 mol % of BH3·THF to the NHC-
Zn-H 18 catalyzed system to promote the hydroboration of
1,1-diborylalkene (Scheme 12b).43
A sequential dehydrogenative boration and double hydro-
boration of terminal aryl and alkyl alkynes enabled by one
catalyst was recently reported by Marder and co-workers. It
was proposed that the catalytic cycle was initiated by the in situ
LnCuH generated from Cu(OAc)2 and monophosphine with
HBpin in the presence of CsF. The formation of a strong F−
Bpin bond might be the driving force for the formation of Cu-
orthogonal reactivities with late transition-metals. In 2020, Wu H, which reacted with terminal alkynes to afford the copper
and co-workers found that the in situ formed Zr-H species acetylide intermediate 31 and H2. σ-bond metathesis of 31
from Cp2ZrCl2/MeOLi in the presence of HBpin was with HBpin afforded 32 and LnCuH. Then, cis-addition of
responsible for the reactivities. Moreover, this system was LnCuH to 32 afforded the alkenyl copper species 33, which
applicable to internal alkenes via a chain-walking mechanism reacted with HBpin via σ-bond metathesis to provide 1,1-
mediated by Zr-H species, which extended the substrate scope diborylalkene 34. Finally, 34 underwent Cu-catalyzed hydro-
for 1,1-diborylalkane synthesis (Scheme 11).42 boration to produce the 1,1,1-tris(boronate) ester (Scheme
13).44
Scheme 11. Zr-Catalyzed 1,1-Diboration of Alkenes
Scheme 13. Copper/Phosphine-Catalyzed Synthesis 1,1,1-
Tris(boronate) Esters from Alkynes
From the aforementioned examples, we can see that an

atom-economialc and direct preparation of 1,1-diborylalkane
from alkenes and borane remains challenging and is worthy of
further exploration.
3. 1,1,1-TRIS(BORONATE) ESTERS
3.1. Synthesis of 1,1,1-Tris(boronate) Esters from
Alkynes. The development of the direct synthesis of 1,1,1-
tris(boronate) esters from alkenes and alkynes has been
relatively slow in comparison with that of other multi-
(boronate) esters, largely due to the increased steric hindrance
ACS Catal. 2021, 11, 1−18
3.2. Synthesis of 1,1,1-Tris(boronate) Esters from direct preparation of vic-bis(boronate) esters from alkynes and
Borylalkenes. The diboration of borylalkenes with B2cat2 alkenes; the boration reagents used were mainly diborons, and
could produce 1,1,1-tris(boronate) esters or 1,1,2-tris- there is only one example using a borane for the direct
(boronate) esters depending on the regioselectivity. Marder hydroboration of a vinyl boronate ester.
and co-workers found that the use of Wilkinson’s catalyst 4.1. Synthesis of Unsaturated vic-Bis(boronate)
mainly afforded the 1,1,1-tris(boronate) esters (Scheme 14).45 Esters from Alkynes. 4.1.1. Transition-Metal-Catalyzed
syn-1,2-Diboration of Alkynes. An alkyne 1,2-diboration was
Scheme 14. Rh-Catalyzed Diboration of Borylalkenes for first reported by Suzuki and Miyaura, who used Pt(PPh3)4 as
Tris(boronate) Ester Synthesis the optimal catalyst (Scheme 16).47 Thereafter, platinum
Scheme 16. Platinum-Catalyzed Diboration of Alkynes
3.3. Synthesis of 1,1,1-Tris(boronate) Esters from

Alkenes. The only reported selective preparation of a 1,1,1-
tris(boronate) ester from an alkene was reported by Huang
Bu
and co-workers using (t PNN)CoCl2 36/NaBEt3H as the
catalyst with B2pin2. Mechanistic studies suggested that the
Co(I)−H catalyst first catalyzed the double dehydrogenative
borylation of alkenes to generate 1,1-diborylalkenes, which
then underwent further hydroboration with HBpin (generated
in situ from Co−H with B2pin2) to afford 1,1,1-triborylalkanes
(Scheme 15).46
Scheme 15. (tBuPNN)CoCl2-Catalyzed 1,1,1-

Tris(boronate) Ester Synthesis from Terminal Alkenes
bis(boryl) complexes 37−39 and [(PPh3)2Pt(η-C2H4)] were

found to be more active than Pt(PPh3)4.48 In general,
platinum-catalyzed diboration of an alkyne follows an insertion
of C−C triple bonds into the Pt−B bond of the platinum
bis(boryl) complex and the subsequent reductive elimination
produces vic-bis(boronate) esters (Scheme 16).49
The application of the unsymmetrical diboron reagent pinB-
Bdan for alkyne diboration reactions has regioselectivity issues.
It has been found that, using Pt(dba) 2 /tris[3,5-bis-
(trifluoromethyl)phenyl]phosphine, the more reactive Bpin
moiety was selectively added to the internal position (Scheme
17a),50 However, interestingly, using a catalytic amount of
Scheme 17. Regioselective Diboration of Alkynes Using

Unsymmetrical Diboron
From the aforementioned examples, we can see that until

now only transition-metal catalysts have been capable of
catalyzing the synthesis of 1,1,1-tris(boronate) esters from
alkenes and alkynes, as normally a metal hydride species, 1,1-
diborylalkenes, and a final hydroboration step are essential for
strict regioselectivity and a metal-free system hardly generate
all the required factors.
LiOH, the Bdan moiety was selectively incorporated at the
4. vic-BIS(BORONATE) ESTERS internal position (Scheme 17b).51 The regioselectivity differ-
vic-Bis(boronate) esters obtained via the selective 1,2- ence between the platinum catalyst and LiOH was mainly
diboration of alkenes or alkynes offer a new platform for the attributed to the activation model difference, as the base (in
construction of 1,2-bifunctional compounds. Furthermore, situ formed alkoxide) interacted preferentially with the more
vinyl vic-bis(boronate) esters are convenient building blocks Lewis acidic Bpin and facilitated the alkyne terminal carbon
for the regio- and stereoselective construction of multi- attack to Bpin.
substituted olefins. Of importance is that the direct preparation Apart from platinum, another successfully applied transition-
of optically pure boronate esters from alkenes could be realized metal in the 1,2-diboration of alkynes was copper, Yoshida and
by applying chiral ligands. In this section, we will discuss the co-workers used Cu(OAc)2 and PCy3 to achieve the 1,2-
ACS Catal. 2021, 11, 1−18
diboration of internal alkynes (Scheme 18a).52 They also Scheme 19. Strategy Developed for the trans-Diboration of
found that the in situ generated arynes could also be diborated Alkynes
Scheme 18. Copper-Catalyzed Diboration of Alkynes
to produce the corresponding vic-diborylarenes (Scheme

18b).52,53 The difference between copper and platinum
catalysts was obvious in the reaction with 1,4-dimethoxy-2-
butyne 40: for [Pt(PPh3)4], the expected diboration product the elimination of nBu3P associated with B−O cleavage
41 was produced, while with copper, 40 was converted afforded α,β-diboryl acrylates 48.
exclusively to 1,2,3,4-tetraboryl-2-butene 42. It was proposed Though the trans-diboration of alkynes was achieved using
that β-oxygen elimination of an alkenyl copper species formed strategy 1, it required activated alkynes and a stoichiometric
2,3-diborylbutadiene, which after 1,4-diboration produced 42 amount of base. A general trans-diboration of unactivated
(Scheme 18c).52 terminal alkynes, such as 1-octyne, was not achieved until
4.1.2. Transition-Metal-Free System for the trans-1,2- Ogawa and co-workers used a photocatalytic method to
Diboration of Alkynes. Alkyne diborations using transition- generate a boryl radical. The use of PPh3 with light irridiation
metal catalysts normally follow the reaction mechanism could improve the trans-selectivity to 95% (Scheme 20).57 The
depicted in Scheme 16; thus, cis-diboration dominates in all boryl radical was proposed to be stabilized by coordination to a
cases and it is difficult to achieve a trans-1,2-diboration process. phosphine. Under photoirradiation, homocleavage of the B−B
Thus, transition-metal-free systems were developed to achieve bond occurred and generated radicals 49 and 50. Radical 50
this goal mainly using two strategies: (1) using heteroatom (O, was thought to be relatively stable than 49. The addition of 49
N) linked alkynes, normally alkynes with a hydroxy or ketone to alkynes afforded the β-boryl-substituted vinyl radical 51,
moiety in the presence of a stoichiometric amount of base followed by homolytic substitution (SH2 reaction) of the vinyl
produce an anionic coordination site which can coordinate radicals with B2pin2.58 The trans-diboration might arise from
with diborons, and by doing so it is expected to reduce the the steric hindrance between the boryl radical and B2pin2
activation energy for trans-diboration; (2) through the (Scheme 20). However, it is noted that even though 95% trans-
formation of a boryl radical. Strategy 1 was best demonstrated selectivity was achieved, the low yield (generally 30−50%) and
by Uchiyama (Scheme 19a),54 Santos (Scheme 19b),55 the use of a high-pressure mercury lamp (500 W) represent the
Sawamura and Ohmiya (Scheme 19c);56 the corresponding main drawbacks of strategy 2 and leave room for further
reaction and activation model are summarized following the exploration.
reaction scheme. For the nBu3P-catalyzed diboration of A temperature-, solvent-, and additive-controlled stereo- and
alkynoates (Scheme 19c), it was proposed that the reaction regioselective diboration of unactivated alkynes was reported
commenced with the conjugate addition of nBu3P to the by Lin and Yamashita. They found that, by simply heating a
alkynoate 43, to form the zwitterionic allenolate 44. The mixture of pinB-BMes2 and phenylacetylene in toluene at 100
terminal boryl group then migrated to the sp-hybridized °C, the cis-adduct 52 was formed as the major product (69%
central carbon of the allene moiety to form ylide intermediates yield) and isomer 53 as the minor product (30% yield).
45/46. Next, the ylide carbon of 46 attacks the boron moiety However, in the presence of a catalytic amount of nBuLi (15
bound to the enolate oxygen to form cyclic borate 47. Finally, mol %), under similar reaction conditions (T = 100 °C for 17
ACS Catal. 2021, 11, 1−18
Scheme 20. Organic Phosphine Catalyzed trans-Diboration Scheme 22. Cu-Catalyzed Selective 1,2-Diboration of
of Unactivated Alkynes under Light Irradiation Alkynes
relatively higher reaction temperature was required, as in the

case of Yun’s system.
A transition-metal-free approach was also developed. In the
presence of 1.5 equiv. of Cs2CO3 and 5 equiv. of MeOH, Song
and co-workers found that various aliphatic alkynes could
selectively diborated in yields of up to 90% at 80 °C (Scheme
23). It was proposed that B2pin2 with methoxide formed the
Scheme 23. Cs2CO3-Catalyzed Selective 1,2-Diboration of

Alkynes
h), 53 was obtained as the major product (61% yield) together

with minor amounts of 52 and trans-isomer 54. Using THF or
n-hexane as the solvent at 70 or 80 °C, or reducing the reaction
temperature to 40 °C in toluene, afforded 54 as the major
product (Scheme 21).59 However, due to the similar reaction
conditions, the relatively lower selectivity was inevitable, which
caused isolation problems.
Scheme 21. Direct and Base-Catalyzed pinB-BMes2

Addition to Alkynes
Lewis acid−base adduct 56, which made the other Bpin moiety
nucleophilic, and it attacked the double bond of vinyl boronate
ester 57. Then, both Bpin moieties attached to the C−C
double bond of 57 to form the 1,1,2-tris(boronate) ester 58.
Finally, in the presence of base, the 1,1,2-tris(boronate)
underwent a protodeboronation process, leading to 1,2-
bis(boronate) esters.62 At lower temperatures, the intermediate
4.2. Synthesis of Saturated vic-Bis(boronate) Esters 58 was selectively obtained, which indicated that the
from Alkynes. The direct diboration of alkynes normally protodeboronation should be the rate-determining step.
gives unsaturated vic-bis(boronate) esters, while the addition 4.3. Synthesis of Saturated vic-Bis(boronate) Esters
of protonic sources such as MeOH could change the product from Borylalkenes. The only example of the use of a borane
to saturated vic-bis(boronate) esters. Copper was found to be for the synthesis of vic-bis(boronate) esters via hydroboration
the most suitable catalyst for this transformation, with the first was reported by Weissensteiner and co-workers using Rh-
example being reported by Hoveyda and co-workers, who used (PPh3)3Cl for the hydroboration of vinyl boronate ester 59
a CuCl/chiral NHC system for the enantioselective production with HBcat. Furthermore, the combination of chiral ligand
of chiral vic-bis(boronate) esters from terminal alkynes with (R)-BINAP and [Rh(COD)2]BF4 afforded 49% 1,2-dibor-
B2pin2 in the presence of MeOH (Scheme 22a).60 Then, Yun ylalkane with 72% ee (Scheme 24a).63 This represents a rare
and co-workers reported the use of a phosphite-copper(I) example of β-site hydroboration of vinyl boronate esters using
system for the diboration of internal-aryl-substituted silylace- a borane. Using a copper catalyst with B2pin2 in the presence
tylenes with B2pin2 (Scheme 22b).61 It is noted that Hoveyda’s of chiral bidentate imidazolinium salt 60, the selective
system working selectively for alkynes might be due to its formation of α-borylalkyl copper 61 and its further trans-
lower reaction temperature, while for internal alkynes a formations in the Pd-catalyzed stereospecific cross-coupling
ACS Catal. 2021, 11, 1−18
Scheme 24. Rh- and Cu-catalyzed vic-bis(boronate) Ester Very recently, Marder and Wu developed a novel system for
Synthesis from Vinyl Boronate Esters the synthesis of cyclopropyl bis(boronate) esters from terminal
alkenes. The reaction proceeded using copper/Xantphos with
B2pin2 as the boron source in the presence of CO (10 bar),
which was eventually incorporated into the product. This work
represents a rare example of the two common reactions of
alkenes: boration and carbonylation in one pot (Scheme 26).75
Scheme 26. Copper-Catalyzed Carbonylative Boration of

Terminal Alkenes
4.4.2. Asymmetric 1,2-Diboration of Alkenes. Unlike 1,1-

diboration, the 1,2-diboration of alkenes normally introduces a
with aryl bromides were recently developed by Yun (Scheme chiral carbon center into the molecules. Thus, transition-metal
24b).64 complexes with different chiral ligands were developed for this
4.4. Synthesis of Saturated vic-Bis(boronate) Esters purpose. For example, Morken and co-workers reported the
from Alkenes. 4.4.1. Transition-Metal-Catalyzed 1,2-Dibo- first catalytic enantioselective diboration of internal alkenes
ration of Alkenes. The first efforts of using a transition-metal using the quinap-derived ligand 62 with (nbd)Rh(acac);
catalyst for the 1,2-diboration of alkenes were carried out by diboration products with up to 35:1 syn:anti diastereoselectiv-
Marder and co-workers using RhCl(PPh3)3 as the catalyst.65 ity and enantioselectivities of up to 98% were observed
However, only up to 44% of the expected products was (Scheme 27a).76 Then the same group used the TADDOL-
obtained. Years later, by using (acac)Rh(dppm) as the catalyst,
a high yield of the 1,2-diboration product was achieved.66
Scheme 27. Transition-Metal-Catalyzed Enantioselective
However, it is worth mentioning that during the studies on
1,2-Diboration of Alkenes
rhodium catalyst they established a highly selective gold system
using AuCl(PEt3) with 2 equiv. of the ligand dcpe (dcpe =
bis(dicyclohexylphosphino)ethane).65
With their wide application in the diboration of alkynes,
platinum complexes such as Pt(dba)2, Pt(NBE)3 (NBE =
norbornene), and Pt(COD)2 (COD = 1,5-cyclooctadiene)
were used for the 1,2-diboration of alkenes without
problems.67 One example that should be highlighted was
that, with a chiral diboron reagent, the corresponding
enantioenriched 1,2-diborylalkane was obtained with up to
60% ee (Scheme 25a).68 Using NHC ligands, Fernández and
co-workers successfully applied a large number of other
transition-metals such as Pt,69 Ag,70 Au,71 Cu,72 Pd,73 and
Ir74 for the 1,2-diboration of alkenes (Scheme 25b).
Scheme 25. Chiral Diboron Reagent and Various NHC-

Transition-Metal Complexes for the 1,2-Diboration of
Alkenes
derived phosphonite ligand 63 to achieve the enantioselective

Pt-catalyzed 1,2-diboration of simple terminal alkenes (Scheme
27b).77 Later on, Nishiyama and co-workers reported the use
of chiral rhodium bis(oxazolinyl)phenyl complexes for the
asymmetric diboration of alkenes. The addition of tBuONa
significantly improved yields and enantioselectivities. In
ACS Catal. 2021, 11, 1−18
addition, unlike the traditional reaction of forming a metal Scheme 29. Ligand- and Substrate-Controlled
bis(boryl) complex, the pinB-RhIII species 64 was proposed to Regioselective Pt-Catalyzed 1,2-Diboration of Alkenes
be formed as a key reactive species (Scheme 27c).78
4.4.3. Transition-Metal-Free System for 1,2-Diboration of
Alkenes. It has been demonstrated that a diboron reagent
could form a Lewis acid−base adduct with a Lewis base,15b,79
which makes the diboron reagent nucleophilic, and transfer
one boryl group to activated olefins.79a,80 Interestingly,
Fernández and co-workers found that a Lewis acid−base
adduct could also be formed with an alkoxide,81 which enabled
two boryl group additions to nonactivated alkenes (Scheme
28a).82 Then, they further introduced chiral alcohols (forming diboration of unsaturated bonds was reported. In 2001, Cheng
and co-workers reported the first Pd-catalyzed diboration of
Scheme 28. Base-Catalyzed 1,2-Diboration of Alkenes in the allenes with the help of a catalytic amount of aryl or alkenyl
Presence of Alcohols iodide to initiate the reaction by forming iodo(pinacolato)
boron 65 (Scheme 30a).88 The first Pd-catalyzed diboration of
Scheme 30. Pd-Catalyzed 1,2-Diboration of Allenes
chiral alkoxides), in efforts to achieve an asymmetric

diboration process. Remarkably, up to 42% ee was achieved
(Scheme 28b).83 Later on, with pinB-Bdan, metal-free
diboration was found to take place with controlled
regioselectivity, and the Bdan unit was installed at the internal
position (Scheme 28c).84 We can see that, in comparison to
the metal-free 1,2-diboration of alkynes, the 1,2-diboration of
alkenes could proceed with a catalytic amount of base,
representing a rare example where a metal-free system give
reactivities similar to those of transition-metal catalysts. The
only drawback probably is the lack of enantioselectivity control
using a metal-free system.
4.5. Synthesis of vic-Bis(boronate) Esters from
Allenes. The ligand effect on the diboration process was
best demonstrated with allene substrates, as both terminal and allenes via a classic oxidative addition of pinB-Bpin to Pd(0)
internal double bonds are likely to be diborated (Scheme for allene diboration was reported by Morken and co-workers
29a).85 Using an unsymmetrical diboron reagent would cause (Scheme 30b).89 They proposed that the formation of 67 by
further selectivity issues. Santos and co-workers found that oxidative addition of B2(pin)2 to the Pd(0) complex was the
Pt(dba)3 and the Sphos ligand could promote the diboration of initial, rate-determining step. Subsequent insertion of the
1,1-diaryl-substituted allenes with pinB-Bdan selectively at the allene ultimately provided the π-allyl complex 68, which then
terminal double bonds, with the Bpin attached to the internal reductively liberated the diboration product. It was noted that
carbon (Scheme 29b).86 the two systems gave different regioselectivities.
Theoretical calculations have shown that the products after 4.7. Synthesis of Unsaturated vic-Bis(boronate)
oxidative addition of diboron to palladium are generally Esters from Alkenes. To obtain unsaturated vic-bis-
unstable.87 Thus, a rare success using palladium for the (boronate) esters from alkenes, a catalyst should have a strong
ACS Catal. 2021, 11, 1−18
enough dehydrogenative boration reactivity. Iwasawa and co- Scheme 32. Pt-Catalyzed Regioselective Diboration of
workers found that the use of the anionic Pd-PSiP-pincer Conjugated Diene
catalyst 69 could achieve this goal. The reaction was initiated
by 69 reacting with AlEt3 to form the Pd-H species 70, which
reacted with B2pin2 to give HBpin and the monoborylpalla-
dium complex 71 bearing a PSiP-pincer ligand. Complex 71
underwent alkene insertion and β-hydride elimination to give
VBE 72 with the regeneration of palladium hydride 70. The
second dehydrogenative boration of 72 in the presence of
excess B2pin2 gave the diboration product 73 or 74, depending
on the alkene substituent (Scheme 31a).90 The substituent
Scheme 31. Catalytic Synthesis of Diborylalkenes from

Alkenes and Diboron
copper/phosphine system for the diboration of CF3-containing

1,3-enynes; interestingly, by a slight change of the ligands,
base, and solvent, regio- and stereodivergent chemoselective
1,3- and 1,4-diboration took place, which produced E-1,3-, Z-
1,3-, and Z-1,4-diborated products on demand (Scheme 33).95
The outcome of this work best demonstrated that the
diboration process is very sensitive to reaction conditions.
Scheme 33. Copper-Catalyzed Divergent Synthesis of 1,3-

and 1,4-Bis(boronate) Esters
effect was also seen in the cobalt system, in which case the
reaction of aryl alkenes with 2 equiv. of B2pin2 in the presence
of 1 equiv. of CsF in DMF selectively produced 1,1-
diborylalkenes, while in the case of alkyl alkenes, cis-1,2-
diborylalkenes were generated (Scheme 31b).91
5. 1,n-BIS(BORONATE) ESTERS (n = 2, 3, 4)
The selective diboration of a 1,3-diene is challenging, as both
1,2- and 1,4-addition are likely to happen. Until now, only one 6. 1,1,2-TRIBORYLALKANES
example achieved the full position addition in the Na2CO3- Morken and co-workers reported the synthesis of chiral 1,1,2-
catalyzed diboration of alkyl-substituted 1,3-dienes (Scheme tris(boronate) esters via 1,2-diboration of vinyl boronate esters
32a).92 Other systems produced either 1,2- or 1,4-diboration with the ligand (R,R)-76. They found that B2cat2 showed
products depending on the catalyst or the geometry of the better enantioselectivity than B2pin2 with 90% ee (Scheme
starting material. For example, in the diboration of penta-1,3- 34a).96 In Song’s report on the base-promoted 1,2-diboration
diene, using Pt(PPh3)3 as the catalyst at 80 °C, only the 1,4- of alkynes, they found that by changing the base from Cs2CO3
addition product was observed. However, with Pt(dba)2, to K2CO3 and the solvent from MeCN to Et2O, at slightly
selective production of the 1,2-addition product was observed lower reaction temperatures (50 °C vs 80 °C), the selective
at room temperature (Scheme 32b).67a,93 Morken and coformation of 1,1,2-triborylalkanes was observed (Scheme
workers found that, for trans-1,3-dienes, selective diboration at 34b).62
the 1,4-position took place, while when the substrates were
changed from trans- to cis-1,3-dienes, selective 1,2-diboration 7. 1,1,3-TRIBORYLALKANES
was observed (Scheme 32c).94 Very recently, Ge and co-workers achieved the first example of
Copper was also used as a catalyst for the synthesis of 1,3- 1,1,3-triboryalkane synthesis via cobalt-catalyzed deoxygenative
and 1,4-bis(boronate) esters. Very recently, Song reported a boration of allylic methyl ethers using HBpin as the boration
ACS Catal. 2021, 11, 1−18
Scheme 34. Synthesis of 1,1,2-Triborylalkanes from Vinyl ized alkynes for the synthesis of 1,1,2-triborylalkenes was only
Boronate Ester and Alkynes achieved by Marder and co-workers using the Cu-
(OAc)2/nBu3P system. Here, 1 equiv. of acrylonitrile was
added to suppress the alkyne hydroboration. Insertion of
alkynylboronate 79 into Cu−B bond generated the alkenyl-
copper species 80, which underwent σ-bond metathesis with
B2pin2 to afford the desired 1,1,2-triborylalkene 81 (Scheme
36b).100
The use of HBpin with terminal alkynes to synthesize 1,1,2-
triborylalkenes was also achieved in a two-pot two-step process
using Ir complex 82. First, the Ir-catalyzed dehydrogenative
boration of terminal alkynes took place to form alkynyl
boronates. Then, treatment of the reaction solution with 1 atm
reagent. Mechanistic studies suggested that this 1,1,3- of CO formed a new catalytic species, which catalyzed the
triborylation reaction proceeds through initial insertion of diboration of alkynyl boronates to 1,1,2-triborylalkenes.101
allylic ether into a Co-Bpin species to form alkylcobalt species However, the 1,1,2-triborylalkenes were only obtained in
77, which contains a β-alkoxy group, the subsequent β-alkoxy moderate yields due to the coproduction of a large amount of
elimination of which produced the branched allyl boronate 78. 1,1-diborylalkenes, which were produced as the main product
Then the cobalt-catalyzed gem-diboration of the resulting allyl without CO treatment. Thus, it is expected that improving the
boronates produced 1,1,3-triborylalkanes (Scheme 35).97 It CO pressure might enhance the selectivity to 1,1,2-
should be noted that certain amounts of 1,1- and 1,3- triborylalkenes (Scheme 37).
diborylakanes and 1,1,2-triborylalkanes were coproduced and
thus moderate yields were obtained. Scheme 37. Ir-Catalyzed Two-Pot Two-Step Process for the
Synthesis of 1,1,2-Triborylalkenes from Terminal Alkynes
Scheme 35. Cobalt-Catalyzed Synthesis of 1,1,3-
Triborylalkanes from Allylic Ethers
9. 1,2,3-TRIS(BORONATE) ESTERS
8. 1,1,2-TRIBORYLALKENES Fernández and co-workers found that the selective production
Srebnik and co-workers used Pt(PPh3)4 as a catalyst for the of 1,2,3-tris(boronate) esters was achieved via a base-catalyzed
diboration of 1-alkynylboronates to produce 1,1,2-triborylal- 1,4-hydroboration of 1,3-dienes, followed by diboration of the
kenes.98 Nishihara extended the substrates to alkynyl MIDA in situ generated allyl boronate ester (Scheme 38a).92 When
(N-methyliminodiacetic acid) boronates and obtained 1,1,2-
triboryl-2-phenylethene with two different boron moieties Scheme 38. Base-Catalyzed Synthesis of 1,2,3-
(Scheme 36a).99 Using a diboron reagent with unfunctional- Tris(boronate) Esters
Scheme 36. 1,1,2-Triborylalkene Synthesis from 1-

Alkynylboronates and Alkynes
tertiary allylic alcohols were used as substrates with Cs2CO3,

allyl boronate esters were formed as intermediate; the reaction
also produced 1,2,3-tris(boronate) esters (Scheme 38b).102
In Yoshida’s work on the Cu/PCy3-catalyzed 1,2-diboration
of alkynes, the use of propargylic ethers produced 1,2,3-
tris(boronate) esters via borylcupration and subsequent σ-
bond metathesis of the π-allyl copper intermediates (Scheme
39a).52 Ma and co-workers developed an efficient method for
the preparation of (E)-alken-1,2,3-tris(boronate) esters from
ACS Catal. 2021, 11, 1−18
Scheme 39. Catalytic Synthesis of 1,2,3-Tris(boronate) then underwent a second B−B activation to afford the 1,1,2,2-
Esters from Propargylic Ethers and Carbonates tetrakis(boronate) ester (Scheme 41).105
Scheme 41. nBuLi- and UV-Light-Promoted Quadruple

Boration of Terminal Alkynes
propargylic carbonates via the 1,2-allenyl boronate intermedi-

ates 83 and their subsequent diboration (Scheme 39b).103
10. TETRA(BORONATE) ESTERS 11. SUMMARY AND OUTLOOK

In their early studies on the platinum-catalyzed diboration of Multi(boronate) esters are emerging as valuable reagents due
alkynes, Marder and co-workers already found that the to their diverse synthetic value and wide range of applications.
addition of diboron to 1,3-diynes could produce tetra- Catalytic systems based on transition-metals, organophos-
(boronate) ester compounds (Scheme 40a).49 Then in 2018, phines, bases, and even catalyst-free systems, with heat or with
light irradiation for the direct synthesis of multi(boronate)
Scheme 40. Copper-Catalyzed Tunable Multi(boronate) esters from abundant alkenes and alkynes, have been
Ester Synthesis from gem-Difluoroalkenes developed over the past 30 years. A large variety of
synthetically useful building blocks from bis- to tetra-
(boronate) esters with different positional relationships of
the adjacent boron moieties have been obtained. In Scheme
42, we outline the reported route from simple alkenes and
Scheme 42. Outline of Multi(boronate) Ester Synthesis

from Alkenes and Alkynes
Shi and co-workers reported the copper-catalyzed boration of

gem-difluoroalkenes with B2pin2 via dual C−F bond cleavage
for the synthesis of tetra(boronate) esters. In addition, they
found that, by slightly altering the reaction conditions from
t
BuOLi to MeOLi and the protonic additive from MeOH to
HCOOH, multi(boronate) esters including 1,2-bis(boronate) alkynes to multi(boronate) esters with blue arrows and those
esters, 1,1,2-tris(boronate) esters, and 1,1,1,2-tetra(boronate) that have not been achieved but are theoretically possible with
esters were selectively obtained (Scheme 40b).104 purple arrows. It should be noted that this is just a simplified
Nagashima and Uchiyama recently found that the in situ ate scheme with simple terminal alkenes and alkynes, as the use of
complex 84 generated from terminal alkynes with nBuLi and unsymmetrical diborons and reactions with allenes, dienes, or
B2pin2 under UV light irradiation enabled the first direct other unsaturated starting materials are not included. However,
quadruple boration of terminal alkynes. UV light and nBuLi several remarks can be made with regard to this scheme. (1)
were crucial for the transformation of aryl alkynes. Mechanistic The reaction relies mainly on hydroboration and diboration
studies revealed that, after the formation of ate complex 84, processes or both processes in one pot. (2) Dehydrogenative
photoinduced B−B activation and C−B bond formation took boration is a promising but relatively less developed process to
place to form 85, which was immediately trapped by excess expand the route to multi(boronate) esters. (3) The starting
B2pin2 to give the borate intermediate 86; intermediate 86 material is very decisive, as more unsaturated substrates offer
ACS Catal. 2021, 11, 1−18
more possibilities; thus, the use of alkynes provides more and technologies for multi(boronate) ester synthesis is
diversity. This was also the case for allenes and dienes, which believed to bring novel advances in this field.
■
could expand the scope of multi(boronate) esters. (4) The
multiboronation processes are very sensitive to the reaction AUTHOR INFORMATION
conditions, as most multi(boronate) esters share common Corresponding Authors
intermediates, while slightly altering the reaction conditions Chungu Xia − State Key Laboratory for Oxo Synthesis and
leads to different products. Selective Oxidation, Suzhou Research Institute of LICP,
Notwithstanding the above achievements, challenges and Lanzhou Institute of Chemical Physics (LICP), Chinese
opportunities still lie ahead, leaving room for further Academy of Sciences, Lanzhou 730000, People’s Republic of
investigation. China; Email: [email protected]
(1) The substrates scope remains limited: from a substrate Lipeng Wu − State Key Laboratory for Oxo Synthesis and
point of view, we know that the degree of unsaturation is Selective Oxidation, Suzhou Research Institute of LICP,
a key factor to determine how many boron moieties can Lanzhou Institute of Chemical Physics (LICP), Chinese
be introduced. More complicated unsaturated hydro- Academy of Sciences, Lanzhou 730000, People’s Republic of
carbons are expected to introduce more possibilities. China; orcid.org/0000-0003-0583-4832;
Thus, substrates such as 1,6-allenynes, unbranched Email: [email protected]
polyenes, branched dendralenes, and even radialenes Authors
could be used in the multiboration systems. Also, Xianjin Wang − State Key Laboratory for Oxo Synthesis and
multiboration of aromatic double bonds such as pyridine Selective Oxidation, Suzhou Research Institute of LICP,
or even benzene is to be realized. Lanzhou Institute of Chemical Physics (LICP), Chinese
(2) Products with more boron moieties are needed: we can Academy of Sciences, Lanzhou 730000, People’s Republic of
see that increasing the number of boron moieties China; University of Chinese Academy of Sciences, Beijing
introduces more challenges concerning chemo- and 100049, People’s Republic of China
regioselectivities. Hence, whereas a large number of Yue Wang − State Key Laboratory for Oxo Synthesis and
studies have focused on the synthesis of bis(boronate) Selective Oxidation, Suzhou Research Institute of LICP,
esters, the development of tris- and tetra(boronate) Lanzhou Institute of Chemical Physics (LICP), Chinese
esters or even more boron moieties has been much less Academy of Sciences, Lanzhou 730000, People’s Republic of
advanced and is expected to provide new and promising China
molecules for materials science. In addition, we can see Wei Huang − CAS Key Laboratory of Bio-based Materials,
that several multi(boronate) esters share common Qingdao Institute of Bioenergy and Bioprocess Technology,
intermediates, which also means that the interconver- Chinese Academy of Sciences, Qingdao 266101, People’s
sions of some multi(boronate) esters are possible, a field Republic of China; orcid.org/0000-0003-2271-5974
that is underdeveloped now. Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.0c03418
(3) Novel catalysts, catalytic systems, and technologies have
yet to be investigated. (a) Hydroboration and boration Author Contributions
are currently the most used reactions, while dehydrogen- The perspective was written through the contributions of all
ative boration opens up new opportunities to access new authors. All authors have approved the final version of the
molecules. Thus, new catalytic systems are needed to manuscript.
promote the dehydrogenative boration process, which is
less favorable than the hydroboration process. (b) Funding
Although the use of chiral ligands for the preparation We are grateful to the Natural Science Foundation of Jiangsu
of optically pure multi(boronate) esters has been Province (BK20180246), the “Innovation & Entrepreneurship
realized, the reaction is generally limited to vic- Talents Plan” of Jiangsu Province, and the National Natural
diboration. Thus, the direct synthesis of chiral tris, Science Foundation of China (21901247, 91845108,
tetra, or even more complicated multi(boronate) esters 21902167) for generous financial support.
is still required. (c) Even though metal-free multi- Notes
The authors declare no competing financial interest.
■
boration of alkenes and alkynes has been reported, the
development of inexpensive transition-metal systems,
such as those of iron, copper, and titanium, is still ACKNOWLEDGMENTS
desirable because such approaches may allow stereo- We thank the Lanzhou Institute of Chemical Physics and the
selective control when the metal is complexed with State Key Laboratory for Oxo Synthesis and Selective
chiral ligands. (d) A tandem reaction involving multi- Oxidation for supporting our research.
boration and further transformations without isolation of
the multi(boronate) esters is a promising strategy to
extend the synthetic application, as some multi-
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Direct Synthesis of Multi(boronate) Esters from Alkenes and Alkynes

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ABSTRACT: Multi(boronate) esters have been attracting increasing attention as

1. INTRODUCTION manner, which allows the production of a large range of

Received: August 5, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acscatal.0c03418

direct (catalytic or stoichiometric) synthesis of multi- Scheme 2. Transition-Metal-Catalyzed 1,1-Diboration of

Scheme 4. Synthesis of 1,1-Diborylalkanes from Alkynes via

From the aforementioned examples, we can see that

Scheme 7. Rh-Catalyzed Synthesis of 1,1-Diborylalkene

Scheme 12. One-Pot Two-Step Synthesis of 1,1,1-

strategy of combining two catalysts for the synthesis of 1,1,1-

From the aforementioned examples, we can see that an

Scheme 16. Platinum-Catalyzed Diboration of Alkynes

3.3. Synthesis of 1,1,1-Tris(boronate) Esters from

Scheme 15. (tBuPNN)CoCl2-Catalyzed 1,1,1-

bis(boryl) complexes 37−39 and [(PPh3)2Pt(η-C2H4)] were

Scheme 17. Regioselective Diboration of Alkynes Using

From the aforementioned examples, we can see that until

Scheme 18. Copper-Catalyzed Diboration of Alkynes

to produce the corresponding vic-diborylarenes (Scheme

relatively higher reaction temperature was required, as in the

Scheme 23. Cs2CO3-Catalyzed Selective 1,2-Diboration of

h), 53 was obtained as the major product (61% yield) together

Scheme 21. Direct and Base-Catalyzed pinB-BMes2

Scheme 26. Copper-Catalyzed Carbonylative Boration of

4.4.2. Asymmetric 1,2-Diboration of Alkenes. Unlike 1,1-

Scheme 25. Chiral Diboron Reagent and Various NHC-

derived phosphonite ligand 63 to achieve the enantioselective

Scheme 30. Pd-Catalyzed 1,2-Diboration of Allenes

chiral alkoxides), in eﬀorts to achieve an asymmetric

Scheme 31. Catalytic Synthesis of Diborylalkenes from

copper/phosphine system for the diboration of CF3-containing

Scheme 33. Copper-Catalyzed Divergent Synthesis of 1,3-

Scheme 36. 1,1,2-Triborylalkene Synthesis from 1-

tertiary allylic alcohols were used as substrates with Cs2CO3,

Scheme 41. nBuLi- and UV-Light-Promoted Quadruple

propargylic carbonates via the 1,2-allenyl boronate intermedi-

10. TETRA(BORONATE) ESTERS 11. SUMMARY AND OUTLOOK

Scheme 42. Outline of Multi(boronate) Ester Synthesis

Shi and co-workers reported the copper-catalyzed boration of

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