异常温和的α-氟丙烯酸酯高产率合成法。

Exceptionally mild, high-yield synthesis of alpha-fluoro acrylates.

作者信息

Zajc Barbara, Kake Shivani

机构信息

Department of Chemistry, The City College and The City University of New York, 138th Street at Convent Avenue, New York, New York 10031, USA.

出版信息

Org Lett. 2006 Sep 28;8(20):4457-60. doi: 10.1021/ol0616236.

DOI:10.1021/ol0616236

PMID:16986924

Abstract

Novel achiral and chiral alkyl alpha-(1,3-benzothiazol-2-ylsulfonyl)-alpha-fluoroacetates can be readily synthesized by metalation-fluorination of (1,3-benzothiazol-2-ylsulfonyl)acetates. DBU-mediated condensations of these fluorinated synthons with aldehydes proceed in a facile manner at 0 degrees C or at room temperature giving high yields of alpha-fluoro acrylates. Ketones are unreactive under these conditions. The presence of fluorine renders the synthon substantially more reactive compared to the unfluorinated analogue. Reactivity of alpha-(1,3-benzothiazol-2-ylsulfonyl)-alpha-fluoroacetate and the Horner-Wadsworth-Emmons reagent (EtO)2P(O)CHFCOOEt has also been compared.

摘要

新型非手性和手性α-(1,3-苯并噻唑-2-基磺酰基)-α-氟乙酸酯可通过(1,3-苯并噻唑-2-基磺酰基)乙酸酯的金属化-氟化反应轻松合成。这些氟化合成子与醛在DBU介导下于0℃或室温下顺利缩合，生成高产率的α-氟丙烯酸酯。酮在这些条件下无反应性。与未氟化的类似物相比，氟的存在使合成子的反应性大大提高。还比较了α-(1,3-苯并噻唑-2-基磺酰基)-α-氟乙酸酯与霍纳-沃兹沃思-埃蒙斯试剂(EtO)2P(O)CHFCOOEt的反应性。