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. 2015 Aug 21;19(8):974-981.
doi: 10.1021/acs.oprd.5b00169. Epub 2015 Jul 2.

Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Cyclic Electrophiles

Samantha E Shockley  1 , Jeffrey C Holder  1 , Brian M Stoltz  1
Affiliations

Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Cyclic Electrophiles

Samantha E Shockley et al. Org Process Res Dev. .

Abstract

This account describes our laboratory's efforts in the development of a palladium-catalyzed asymmetric conjugate addition of arylboronic acids to cyclic conjugate acceptors. Specifically, we highlight the study of this transformation in the following areas: (a) construction of all-carbon quaternary stereocenters, (b) elucidation of the reaction mechanism,

Keywords: asymmetric; catalysis; conjugate addition; palladium.

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Figures

Figure 1
Figure 1
Linear relationship of catalyst ee to product ee
Figure 2
Figure 2
Proposed catalytic cycle for the asymmetric conjugate addition of arylboronic acids to cyclic enones catalyzed by the combination of Pd(OCOCF3)2 and (S)-t-BuPyOx
Figure 3
Figure 3
Calculated transition states and effect of α′-substituents on enantioselectivity
Figure 4
Figure 4
Hammett plot of log10(er) vs σp for select arylboronic acids
Scheme 1
Scheme 1
Transition metal catalyzed asymmetric conjugate addition
Scheme 2
Scheme 2
Palladium-catalyzed asymmetric conjugate addition with (S)-t-BuPyOx (3)
Scheme 3
Scheme 3
Water is required to balance the reaction equation
Scheme 4
Scheme 4
Synthetic approach to taiwaniaquinoid terpene natural products by palladium-catalyzed asymmetric conjugate addition
See this image and copyright information in PMC

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