Pouy Mark J, Stanley Levi M, Hartwig John F
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
J Am Chem Soc. 2009 Aug 19;131(32):11312-3. doi: 10.1021/ja905059r.
Highly enantioselective, iridium-catalyzed monoallylations of ammonia are reported. These reactions occur with electron-neutral, -rich, and -poor cinnamyl carbonates, alkyl and trityloxy-substituted allylic carbonates, and dienyl carbonates in moderate to good yields and excellent enantioselectivities. This process is enabled by the use of an iridium catalyst that does not require a Lewis acid for activation and that is stable toward a large excess of ammonia. This selective formation of primary allylic amines allows for one-pot syntheses of heterodiallylamines and allylic amides that are not otherwise accessible via iridium-catalyzed allylic amination without the use of blocking groups and protective group manipulations.
报道了铱催化的氨的高度对映选择性单烯丙基化反应。这些反应适用于电子中性、富电子和缺电子的肉桂酸酯、烷基和三苯氧基取代的烯丙基碳酸酯以及二烯基碳酸酯，产率适中至良好，对映选择性优异。该过程通过使用一种铱催化剂得以实现，该催化剂不需要路易斯酸活化，并且对大量过量的氨稳定。伯烯丙基胺的这种选择性形成使得能够一锅法合成杂二烯丙基胺和烯丙基酰胺，而在不使用保护基和保护基操作的情况下，通过铱催化的烯丙基胺化反应无法以其他方式获得这些产物。
