手性氟烯炔的立体选择性合成。
Stereoselective synthesis of conjugated fluoro enynes.
机构信息
Department of Chemistry, The City College and The City University of New York, 160 Convent Avenue, New York, New York 10031, United States.
出版信息
J Org Chem. 2012 Oct 5;77(19):8417-27. doi: 10.1021/jo300971w. Epub 2012 Sep 24.
Abstract
Metalation-electrophilic fluorination of TMS- and TIPS-protected 1,3-benzothiazol-2-yl (BT) propargyl sulfones gave corresponding BT fluoropropargyl sulfones, Julia-Kocienski reagents for the synthesis of fluoro enynes. Both reagents reacted with aldehydes under mild DBU- or LHMDS-mediated conditions, giving high yields of conjugated fluoro enynes with E-stereoselectivity. In comparison to DBU-mediated reactions, stereoselectivity was higher in low-temperature LHMDS-mediated reactions. Two ketones were shown to react as well, using LHMDS as base. In situ removal of the TMS group gave terminal conjugated 2-fluoro 1,3-enynes. Synthetic utility of the fluoro enynes was demonstrated by conversion to internal alkynes and to stereoisomeric fluoro dienes via Sonogashira and Heck couplings.
摘要
TMS-和 TIPS 保护的 1,3-苯并噻唑-2-基（BT）丙炔基砜的金属化-亲电氟化生成相应的 BT 氟丙炔基砜，这是合成氟代烯炔的 Julia-Kocienski 试剂。这两种试剂在温和的 DBU-或 LHMDS 介导条件下与醛反应，以高收率得到具有 E-立体选择性的共轭氟代烯炔。与 DBU 介导的反应相比，低温 LHMDS 介导的反应具有更高的立体选择性。使用 LHMDS 作为碱，两种酮也可以反应。通过原位脱除 TMS 基团得到末端共轭 2-氟-1,3-烯炔。通过 Sonogashira 和 Heck 偶联反应将氟代烯炔转化为内部炔烃和立体异构的氟代二烯，证明了氟代烯炔的合成实用性。
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