cs1c02723_si_005.cif (355.82 kB)
Highly Enantio- and Diastereoselective Synthesis of 1,2,3-Trisubstituted Cyclopropanes from α,β-Unsaturated Amides and Stabilized Sulfur Ylides Catalyzed by a Chiral Copper(I) Complex
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posted on 2021-09-03, 12:37 authored by Santosh K. Pagire, Naoya Kumagai, Masakatsu ShibasakiThe
stereoselective preparation of 1,2,3-substituted cyclopropanes
from α,β-unsaturated carbonyl compounds in the carboxylic
acid oxidation state through Michael addition-initiated ring-closure
reactions is a significant challenge in organic synthesis. Herein,
the previously elusive catalytic asymmetric cyclopropanation of α,β-unsaturated
amides with stabilized sulfur ylides has been efficiently accomplished
utilizing a chiral Cu(I) complex. This Lewis acid catalytic system
effectively converts a wide range of electron-deficient alkenes into
the corresponding 1,2,3-trisubstituted cyclopropanes under mild reaction
conditions in good to excellent yields with both high to excellent
enantio- and diastereoselectivities. The resulting enantiomerically
enriched cyclopropane amides can be readily diversified into promising
synthetic intermediates such as β-aminocyclopropanecarboxylic
acids with the facile recovery of the 7-azaindoline auxiliary without
influencing the optical purity of the cyclopropane unit, which highlights
the synthetic efficacy of this catalytic approach.
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stabilized sulfur ylidesmild reaction conditionsefficiently accomplished utilizingunsaturated carbonyl compoundspromising synthetic intermediateschiral cu (unsaturated amidessynthetic efficacychiral copperwide rangetrisubstituted cyclopropanessubstituted cyclopropanesstereoselective preparationsignificant challengereadily diversifiedorganic synthesisoptical puritymichael additioninitiated ringhighly enantiofacile recoveryexcellent yieldsexcellent enantiodiastereoselective synthesisdeficient alkenescyclopropane unitclosure reactionscatalytic approachaminocyclopropanecarboxylic acids