Abstract
One of the major challenges of modern asymmetric catalysis is the ability to selectively control the formation of all diastereoisomers of reaction products possessing multiple stereocenters. Pioneers of such diastereodivergent catalytic asymmetric processes have focused on reactions where the newly formed stereogenic centres are proximal to the active carbonyl group. To date, however, diastereodivergent reactions at remote positions remain an unmet challenge. Herein, we describe a catalyst-controlled diastereodivergence in the formation of remote stereocenters in the direct vinylogous Michael reactions of β, γ-unsaturated butenolides to α, β-unsaturated ketones. The reactions are enabled by two complementary, non-enantiomeric multifunctional catalysts, which mutually activate and organise both reactants, affording either the syn- or anti-adduct with high diastereo- and enantioselectivity. These two catalytic systems are also applicable in the Mukaiyama-Michael reactions and tandem Michael-Michael reactions.
Highlights
One of the major challenges of modern asymmetric catalysis is the ability to selectively control the formation of all diastereoisomers of reaction products possessing multiple stereocenters
We present our development of the first example of a highly diastereodivergent, asymmetric and direct vinylogous Michael reactions of b, g-unsaturated butenolides to a, b-unsaturated ketones, generating both anti- and syn-adducts by employing complementary, non-enantiomeric primary amine catalytic systems
In short, we have established new methodologies to control the selective formation of remote stereocenters at g-positions via diastereodivergent catalytic asymmetric processes
Summary
One of the major challenges of modern asymmetric catalysis is the ability to selectively control the formation of all diastereoisomers of reaction products possessing multiple stereocenters Pioneers of such diastereodivergent catalytic asymmetric processes have focused on reactions where the newly formed stereogenic centres are proximal to the active carbonyl group. The reactions are enabled by two complementary, non-enantiomeric multifunctional catalysts, which mutually activate and organise both reactants, affording either the syn- or anti-adduct with high diastereo- and enantioselectivity These two catalytic systems are applicable in the Mukaiyama–Michael reactions and tandem Michael–Michael reactions. We present our development of the first example of a highly diastereodivergent, asymmetric and direct vinylogous Michael reactions of b, g-unsaturated butenolides to a, b-unsaturated ketones, generating both anti- and syn-adducts by employing complementary, non-enantiomeric primary amine catalytic systems
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