醛对作为具有挑战性的迈克尔受体的乙烯基砜和乙烯基膦酸酯的对映选择性有机催化共轭加成反应。
Enantioselective organocatalytic conjugate addition of aldehydes to vinyl sulfones and vinyl phosphonates as challenging Michael acceptors.
作者信息
Sulzer-Mossé Sarah, Alexakis Alexandre, Mareda Jiri, Bollot Guillaume, Bernardinelli Gerald, Filinchuk Yaroslav
机构信息
Department of Organic Chemistry, University of Geneva, 30 Quai Ernest Ansermet, 1211 Geneva, Switzerland.
出版信息
Chemistry. 2009;15(13):3204-20. doi: 10.1002/chem.200801892.
Chiral framework: Chiral amines with pyrrolidine frameworks catalyze the enantioselective conjugate addition of a wide range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee (see scheme). The high versatility of the Michael adducts is exemplified by various functionalizations with conservation of the optical purity.Chiral amines with a pyrrolidine framework catalyze the enantioselective conjugate addition of a broad range of aldehydes to various vinyl sulfones and vinyl phosphonates in high yields and with enantioselectivities up to >99 % ee. This novel process provides synthetically useful chiral gamma-gem-sulfonyl or phosphonyl aldehydes which can be widely functionalized with retention of the enantiomeric excess. Mechanistic insights including DFT calculations are explored in detail.
手性骨架
具有吡咯烷骨架的手性胺催化多种醛对各种乙烯基砜和乙烯基膦酸酯的对映选择性共轭加成反应，产率高，对映选择性高达>99%ee（见示意图）。迈克尔加成物的高度通用性体现在各种官能化反应中，同时保持光学纯度。具有吡咯烷骨架的手性胺催化多种醛对各种乙烯基砜和乙烯基膦酸酯的对映选择性共轭加成反应，产率高，对映选择性高达>99%ee。这一新颖的过程提供了具有合成实用性的手性γ-偕-磺酰基或膦酰基醛，它们可以在对映体过量得以保留的情况下进行广泛的官能化反应。详细探讨了包括密度泛函理论计算在内的机理见解。
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