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New Bifunctional Substrates for Copper‐Catalyzed Asymmetric Conjugate Addition Reactions with Trialkylaluminium
Author(s) -
Ladjel Chehla,
Fuchs Nicolas,
Zhao Jinkai,
Bernardinelli Gérald,
Alexakis Alexandre
Publication year - 2009
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200900662
Subject(s) - chemistry , stereocenter , bifunctional , conjugate , phosphoramidite , enantioselective synthesis , nucleophile , copper , catalysis , michael reaction , reagent , combinatorial chemistry , nucleophilic substitution , medicinal chemistry , stereochemistry , organic chemistry , dna , mathematical analysis , biochemistry , mathematics , oligonucleotide
Trialkylaluminium reagents have been found to undergo a copper‐catalyzed asymmetric conjugate addition (ACA) reaction with oxabicyclo[2.2.1]hepta‐2,5‐diene‐2,3‐dicarboxylates with the simultaneous creation of two stereocenters. Different types of ligands were tested, and chiral phosphoramidite ligands allowed the reaction to proceed with good yields and good to excellent enantioselectivity. The syn substitution product observed by X‐ray analysis suggests an exo attack of the nucleophile. Herein we report the results obtained in the development of this copper‐catalyzed ACA methodology, which affords an all‐carbon quaternary center with unsubstituted and substituted oxacyclic Michael acceptors. The study was completed by mechanistic investigations performed to elucidate the original reaction pathway. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)