Department of Chemistry, The University of Kansas, 1251 Wescoe Hall Drive, Lawrence, Kansas 66045-7582, United States.
J Org Chem. 2013 Jul 19;78(14):7281-7. doi: 10.1021/jo400793a. Epub 2013 Jul 1.
Herein we present the development of asymmetric deacylative allylation of ketone enolates. The reaction directly couples readily available ketone pronucleophiles with allylic alcohols using facile retro-Claisen cleavage to form reactive intermediates in situ. The simplicity and robustness of the reaction conditions is demonstrated by the preparation of >6 g of an allylated tetralone from commercially available materials. Furthermore, use of nonracemic PHOX ligands allows intermolecular formation of quaternary stereocenters directly from allylic alcohols.
在此，我们介绍了酮烯醇化物的不对称去酰基烯丙基化反应的发展。该反应直接将易得的酮亲核试剂与烯丙醇偶联，利用简便的反-Claisen 裂解原位形成反应中间体。反应条件的简单性和稳健性通过从市售原料制备>6g 的烯丙基四氢萘酮得到了证明。此外，使用非手性 PHOX 配体可以使手性醇直接形成季碳立体中心。
