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. 2015 Jun 17;137(23):7290-3.
doi: 10.1021/jacs.5b04289. Epub 2015 Jun 4.

Alkenyl carbonyl derivatives in enantioselective redox relay Heck reactions: accessing α,β-unsaturated systems

Chun Zhang  1 , Celine B Santiago  1 , Lei Kou  1 , Matthew S Sigman  1
Affiliations

Alkenyl carbonyl derivatives in enantioselective redox relay Heck reactions: accessing α,β-unsaturated systems

Chun Zhang et al. J Am Chem Soc. .

Abstract

A highly enantioselective and site-selective Pd-catalyzed arylation of alkenes linked to carbonyl derivatives to yield α,β-unsaturated systems is reported. The high site selectivity is attributed to both a solvent effect and the polarized nature of the carbonyl group, both of which have been analyzed through multidimensional analysis tools. The reaction can be performed in an iterative fashion allowing for a diastereoselective installation of two aryl groups along an alkyl chain.

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Figures

Figure 1
Figure 1
a) Previously reported enantioselective relay Heck reactions of alkenols including mechanistic analysis. b) Proposed new enantioselective relay Heck reaction of alkenes linked to carbonyl derivatives and resultant iterative Heck reaction.
Figure 2
Figure 2
Multidimensional correlation of solvent parameters with site selectivity.
Figure 3
Figure 3
Correlation of observed site selectivity to the NBO charge of the carbonyl oxygen.
See this image and copyright information in PMC

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