Department of Medicinal Chemistry, Institute of Biomaterials and Bioengineering, Tokyo Medical and Dental University, 2-3-10 Kandasurugadai, Tokyo 101-0062, Japan.
Org Lett. 2012 Sep 7;14(17):4490-3. doi: 10.1021/ol301988d. Epub 2012 Aug 17.
A robust and efficient method for the synthesis of trisubstituted (Z)-chloroalkenes is described. A one-pot reaction of γ,γ-dichloro-α,β-enoyl sultams involving organocuprate-mediated reduction/asymmetric alkylation affords α-chiral (Z)-chloroalkene derivatives in moderate to high yields with excellent diastereoselectivity, and allylic alkylation of internal allylic gem-dichlorides is also demonstrated. This study provides the first examples of the use of allylic gem-dichlorides adjacent to the chiral center for novel 1,4-asymmetric induction.
本文描述了一种合成三取代（Z）-氯烯的稳健高效方法。γ,γ-二氯-α,β-烯酰基磺酰胺的一锅反应涉及有机铜介导的还原/不对称烷基化，以中等至高收率和优异的非对映选择性得到α-手性（Z）-氯烯衍生物，并且还证明了内部烯丙基偕二氯化物的烯丙基烷基化。这项研究提供了首例使用手性中心相邻的烯丙基偕二氯化物进行新型 1,4-不对称诱导的实例。
