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Zirconocene catalyzed diastereoselective

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carbometalation of cyclobutenes†
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Cite this: Chem. Sci., 2017, 8, 334

Sudipta Raha Roy, Hendrik Eijsberg, Jeffrey Bruffaerts and Ilan Marek*

Received 15th June 2016 The regio- and diastereoselective zirconocene-catalyzed carbomagnesiation of cyclobutenes is herein
Accepted 4th August 2016
reported to afford configurationally stable cyclobutylmagnesium species that could subsequently react
DOI: 10.1039/c6sc02617f with a large variety of electrophiles to give polysubstituted cyclobutane species as a single diastereoisomer.

www.rsc.org/chemicalscience

disubstituted double bond, several issues, such as: (1) regio-

Introduction and stereoselectivity of the addition; (2) congurational
In the repertoire of strategies using organometallic species stability of the resulting sp3 organometallic species; and (3)
that could lead to the efficient formation of two carbon– diastereoselectivity of the reaction with electrophiles; are of
carbon bonds per chemical step, the carbometalation reaction major concern.7 Finally, the enantioselectivity of the addition
to an unsaturated C–C bond represents a powerful strategy. of a carbon nucleophile across an unactivated double bond
The carbometalation reaction, dened as “the addition of still represents a very challenging problem despite the fact
a carbon–metal bond of an organometallic across a carbon– that it would acquire signicant utility as a method for the
carbon unsaturated system leading to a new organometallic creation of asymmetric vicinal carbon centers (Scheme 1, path
species that can be further functionalized” – is one of the most c).8 Due to the inherent difficulty to achieve an efficient car-
powerful approaches that have been used extensively to bometalation reaction across unactivated alkenes, most of the
perform the 1,2-bis-alkylation of alkynes.1 In this context, studies have focused on strained double bonds. As such, the
organocopper,2 as well as zirconocene-catalyzed methyl- copper-mediated carbometalation reaction of cyclopropenyl
alumination,3 occupies a signicant place due to its high derivatives9 has been investigated in detail to provide a new
stereoselectivity, typically controlled by the nature of the route to enantio- and diastereoenriched congurationally
substituents on the triple bond (Scheme 1, path a for an stable cyclopropyl metal species (Scheme 1, path d).10
example of carbocupration). Besides forming stereodened However, all attempts to extend the concept of carbometala-
polysubstituted double bonds, the carbometalation reaction tion to less-strained compounds such as cyclobutenes failed,
of alkynes has recently been considered as a new stereo- most probably due to the lower energy release during the
dened chemical handle to prepare reactive intermediates for addition step.11 None of the copper-catalyzed carbomagne-
the subsequent creation of more complex molecular struc- siation, copper-catalyzed carbozincation, carbocupration with
tures possessing sp3-congurated stereocenters including organocopper or organocuprate reactions in Et2O or THF
quaternary carbon stereocenters (Scheme 1, path b).4 1,2- could lead to the desired addition of the organometallic
Disubstituted alkyl chains possessing sp3 stereocenters could species across a double bond embedded in a 4-membered ring
theoretically also be obtained through the carbometalation of (Scheme 1, path e).12 Only Tortosa and coworkers recently
appropriate alkenes (Scheme 1, path c).5 However, these reported the highly enantioselective desymmetrization of
transformations are much more challenging than the carbo- meso-cyclobutene through the copper-catalyzed borylation
metalation reactions of alkynes, since the carbometalated reaction.13
product is usually of similar reactivity to the starting organ- As stereodened cyclobutyl metal species en route to poly-
ometallic species and an oligomerization reaction typically substituted cyclobutane derivatives still represent an important
occurs.6 Moreover, when the reaction is performed on the a,b- building block in the eld of small ring chemistry,14 we there-
fore decided to pursuit our efforts to functionalize cyclobutene
species into polysubstituted metalated cyclobutanes through
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry carbometalation reaction, and more particularly through the
and Lise Meitner-Minerva Center for Computational Quantum Chemistry, Dzhemilev reaction. It should be emphasized that all starting
Technion-Israel Institute of Technology, Technion City, Haifa 32000, Israel. E-mail:
cyclobutenes 1 were prepared by a rhodium-catalyzed inter-
[email protected]; Fax: +972-4-829-37-09; Tel: +972-4-829-37-09
† Electronic supplementary information (ESI) available: Experimental procedures,
molecular [2 + 2] cycloaddition of terminal alkynes with elec-
spectroscopic data and copies of 1H and 13C NMR spectra. See DOI: tron-decient alkenes.15
10.1039/c6sc02617f

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Scheme 1 Carbometalation reactions.

Results and discussion magnesium V or cyclobutyl zirconocene species VI aer trans-

metalation. The selectivity of the transmetalation is critical as
In this context, and as alluded previously, we were particularly the carbon attached to the zirconocene will then be subse-
interested in the possibility to reach our goal through the dia- quently reduced to regenerate the catalytic zirconacyclopropane
stereoselective zirconocene-catalyzed carbomagnesiation reac- species I (see for example the preparation of VIII via the
tion (Dzhemilev reaction) as described in Scheme 2.16 reduction depicted in VII). If one assumes that the reaction
In this transformation, the addition of ethylmagnesium would only provide V, then the cyclobutyl magnesium derivative
bromide to a catalytic amount of dichlorobis(h5-cyclo- VIII may be expected, whereas if the transmetalation occurs to
pentadienyl)zirconium(IV) [Cp2ZrCl2] should provide the zirco- provide VI, the cyclobutyl ethylmagnesium species IX is antici-
nacyclopropane I that would react in situ with the double bond pated. Finally, if one still assumes that the catalytic cycle would
of the cyclobutene 1 to form either the addition product II or III. only provide VIII, the congurational stability of this cyclobutyl
Each of these two possible regioisomers could be present as magnesium species as well as its reactivity towards electrophiles
potentially two diastereoisomers (II anti versus II syn and III anti needs to be investigated in detail.
versus III syn). So, not only the regioselectivity of the zircono- Therefore, the Dzhemilev ethylmagnesiation of cyclobutene
cene-catalyzed carbomagnesiation of substituted cyclobutene 1 catalyzed by dichlorobis(h5-cyclopentadienyl)zirconium(IV)
should be controlled (II versus III) but also the diaster- proceeds by a rather convoluted process with potentially several
eoselectivity of the reaction (syn versus anti). Assuming that cyclic intermediates and the unique formation of VIII, requiring
from the four possible regio- and diastereoisomers only the a complete control of all the elementary steps. We initially
isomer II anti will be produced, the reaction of ethylmagnesium focused our attention on the diastereoselective zirconocene-
bromide with the zirconacyclopentane II anti would then mediated carbomagnesiation of cyclobutene 1a (R1 ¼ (CH2)2Ph,
provide the ate-complex IV that may either lead to the cyclobutyl R2 ¼ Me) in THF and we were pleased to observe that the

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Scheme 2 Proposed zirconocene-catalyzed diastereoselective ethylmagnesiation reaction of cyclobutene.

addition reaction proceeds selectively under mild conditions regioisomer III (II anti : III syn ¼ 87 : 13, not shown in Scheme
(25  C, 12 h) to provide 2a in 82% isolated yield with >98 : 2 3). Now that the regio- and diastereoselectivity of the zircono-
diastereoselectivity (Scheme 3). The relative conguration of cene-catalyzed ethylmagnesiation reaction of cyclobutene 1a is
cyclobutane 2a was determined by the Nuclear Overhauser controlled, we were interested to understand the following step,
Effect (NOE) and from this analysis, we could conrm that the namely the transmetalation step, and determine if cyclo-
zirconocene-catalyzed ethylmagnesiation is not only highly butylmagnesium species VIII or its ethyl metalated cyclobutyl
regioselective (formation of II versus III in a 92 : 8 ratio) but also isomer IX would be formed. To answer this question, treatment
fully anti-diastereoselective (unique formation of II anti versus II of 1a with ZrCp2Cl2 (20 mol%) and ethylmagnesium bromide
syn, Scheme 2). As the reaction of a cyclobutene possessing an was stirred at room temperature overnight and quenched with
ether group (1a, R1 ¼ (CH2)2Ph, R2 ¼ Me) or an alcohol (1b, D2O/DCl. The cyclobutane 2c was selectively obtained in 80%
R1 ¼ (CH2)2Ph, R2 ¼ H) could potentially present a comple- yield as a unique diastereoisomer (Scheme 3) suggesting
mentary sense of stereoinduction (reversal of stereoselectivity complete selectivity in the transmetalation reaction. Only the
due to association of magnesium alkoxides with the zircono- cyclobutylmagnesium bromide VIII was therefore obtained
cene reagent),17 the same reaction was performed with 1b and through the reduction depicted in VII. Similarly, when the
the product 2b was obtained with the same diastereoisomeric intermediate cyclobutylmagnesium species was trapped with I2
ratio and with the same relative conguration albeit in slightly or NBS, 2d and 2e were isolated in 67% and in 58% yield,
lower yield (64%, 2b was then transformed into 2a and the respectively, in an excellent diastereoisomeric ratio. The relative
stereochemistry was corroborated). conguration of the cyclobutane 2d was determined by NOE
Therefore, the uniform sense of stereoinduction of the (see ESI†).
reaction with 1a and 1b implies that the reaction is fully The unique stereochemistry of these functionalized cyclo-
controlled by steric factors. Decreasing the basicity of the butanes indicates that the cyclobutylmagnesium bond is
reaction medium and using Et2O as solvent instead of THF does congurationally stable at room temperature under this exper-
not change the stereochemical outcome of the reaction and the imental condition. As the rate for inversion of conguration of
major isomer 2a was still observed with, however, higher the C–MgBr should be higher for cyclobutyl than for cyclo-
quantity of product resulting from the formation of the opposite propyl, we were interested to check if the inversion of the

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Scheme 3 Zirconocene-catalyzed diastereoselective ethylmagnesiation reaction of cyclobutene and reaction with electrophiles.

organometallic species of 2MgBranti into 2MgBrsyn (Scheme 3, addition of CuI and LiCl (10 and 20 mol% respectively) at 0  C
path b) could occur at higher temperature, as a chelated system for 15 min. Then, addition of allylbromide at 0  C provided the
would be preferentially formed. When the zirconocene-cata- allylated product 2f in 72% yield with the same diastereoiso-
lyzed ethylmagnesiation reaction was performed on 1a meric ratio of 98 : 2 : 0 : 0. The relative conguration of the
(R1 ¼ (CH2)2Ph, R2 ¼ Me) at room temperature for 12 h in THF cyclobutane 2f was determined by NOE and indicates that the
followed by warming at 55  C for 1 h and nally quenching with transmetalation reaction proceeds with retention of congura-
I2, the same isomer 2d was obtained with an identical diaste- tion to lead to a congurationally stable cyclobutyl carbon–
reoisomeric ratio suggesting that the cyclobutylmagnesium copper bond.20 The transmetalation reaction was also per-
bromide species is congurationally stable despite the potential formed on the intermediate resulting from the zirconocene-
stabilizing intramolecular chelation (Scheme 3, path b). The catalyzed carbomagnesiation reaction on alcohol 1b
same congurational stability was observed when the isomeri- (R1 ¼ (CH2)2Ph, R2 ¼ H) to check if a potential reversal of
zation was tested on 1d (R1 ¼ Hex, R2 ¼ H). stereoselectivity with the copper salt may occur due to associa-
Having a congurationally stable C–MgBr bond in the tion with magnesium alkoxide. Further addition of allylbromide
cyclobutylmagnesium bromide structure VIII, we were then leads to the same major diastereoisomer 2g in slightly lower
concerned by the stereochemistry of transmetalation with ratio but still indicating that the transmetalation proceeds
copper salt. Would the resulting cyclobutylcopper species be again with retention of conguration and that the C–Cu bond is
produced with retention18 or inversion19 of conguration and congurationally stable. The reaction is not restricted to allyl-
would it also present some congurational stability? Thus, to bromide and a functionalized electrophile could also be added
the intermediate VIII, prepared as previously described from 1a successfully (formation of 2h) with similar diastereoisomeric
with ZrCp2Cl2 (20 mol%) and ethylmagnesium bromide, the ratio and yield. For functionalization with a sp2-carbon center,
corresponding cyclobutylcopper species was obtained by an additional transmetalation to Pd is required and 2i could be

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