结合
螯合作用
醇盐
立体中心
试剂
脱质子化
化学
烷基
加成反应
组合化学
药物化学
立体化学
有机化学
对映选择合成
离子
催化作用
数学
数学分析
作者
Fraser F. Fleming,Qunzhao Wang,Zhe Zhang,Omar W. Steward
摘要
Temporarily anchoring Grignard and organolithium reagents to gamma-hydroxy-alpha,beta-alkenenitriles promotes efficient conjugate additions to what are otherwise recalcitrant Michael acceptors. Sequential deprotonation and addition of a modest excess of a second Grignard reagent allows effective conjugate delivery of alkyl groups to cyclic and acyclic alkenenitriles. Mechanistically, conjugate additions proceed through alkylmagnesium alkoxide complexes for all but the more substituted alkenenitriles that require alkyl transfers from the more reactive ate complexes. Synthetically, chelation-controlled conjugate additions rapidly, and stereoselectively, assemble substituted nitriles, installing up to two new stereocenters in a single synthetic operation.
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