Epimerization and kinetic resolution in copper-catalyzed enantioselective 1,4-additions of organozinc reagents to 6-substituted cyclohex-2-enones
摘要:
Enantioselective 1,4-addition reactions of diethyl-, dimethyl-, and di-n-butylzinc to 6-methylcyclohex-2-enone ( 1 ) and 6-t-butylcyclohex-2-enone ( 4 ), catalyzed by Cu(OTf) 2 and phosphoramidites L1 – L4 were examined. The additions to enone 1 proceeded with high enantioselectivity; by acid- or base-catalyzed epimerization, adduct (S,S)- 2 can be obtained from racemic 1 in diastereo- and enantiomerically pure form. In contrast, Michael additions to substrate 4 were rather slow and could be used for the kinetic resolution of the enone.
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关键词:
copper catalysis enantioselectivity epimerization kinetic resolution Michael addition phosphoramidites
DOI:
10.1016/S0040-4039(02)01898-1
年份:
2002
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