Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco/Euskal Herriko Unibertsitatea (UPV/EHU), P.O. Box 644, E-48080 Bilbao, Spain.
J Am Chem Soc. 2012 Jul 25;134(29):11872-5. doi: 10.1021/ja3041042. Epub 2012 Jul 16.
Donor-acceptor monosubstituted hydrazones participate as suitable reagents able to undergo an enantioselective formal diaza-ene reaction with α,β-unsaturated aldehydes under chiral secondary amine catalysis. This constitutes a new approach for the enantioselective conjugate addition of hydrazones to enals under metal-free conditions and leads to the formation of γ-hydrazono carboxylic acids after oxidation/[1,3]-H shift. The methodology is also useful for the synthesis of enantioenriched β-substituted α-keto-1,5-diesters by using the hydrazone moiety as a masked carbonyl group.
供体-受体单取代腙作为合适的试剂参与其中，能够在手性仲胺催化下与α,β-不饱和醛经历对映选择性的形式二氮烯-ene 反应。这为无金属条件下腙与烯醛的对映选择性共轭加成提供了一种新方法，并且在氧化/[1,3]-H 迁移后形成γ-腙基羧酸。该方法也可用于通过将腙部分作为掩蔽羰基来合成对映体富集的β取代的α-酮-1,5-二酯。
