Premium
Gram‐Scale Synthesis of β‐(Hetero)arylethenesulfonyl Fluorides via a Pd(OAc) 2 Catalyzed Oxidative Heck Process with DDQ or AgNO 3 as an Oxidant
Author(s) -
Zha GaoFeng,
Bare Grant A. L.,
Leng Jing,
Shang ZhenPeng,
Luo Zhixiong,
Qin HuaLi
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201700688
Subject(s) - chemistry , heck reaction , chemoselectivity , aryl , catalysis , organic chemistry , combinatorial chemistry , boronic acid , suzuki reaction , anhydrous , oxidative coupling of methane , acceptor , palladium , alkyl , physics , condensed matter physics
A practical oxidative Heck reaction between organoboronic acids and ethenesulfonyl fluoride (ESF) is developed. Aryl‐ and heteroaryl‐boronic acids react efficiently and stereoselectively with ESF in the presence of a catalytic amount of Pd(OAc) 2 and 2,3‐dichloro‐5,6‐dicyano‐ p ‐benzoquinone (DDQ) or AgNO 3 in AcOH to afford the corresponding E ‐isomer of β‐arylethenesulfonyl fluoride products. The utility of this reaction is exemplified by an expanded scope of 47 examples including N‐, O‐, and S‐containing heteroaromatics, demonstrating chemoselectivity over aryliodides, and gram‐scale operation without the requirement for strict anhydrous or oxygen‐free conditions. Furthermore, this procedure discriminates against the formation of arylboronic acids homo‐coupling byproducts. In addition, the preparation of the first aryl vinylsulfonate polymer, a material with functionalizable Michael acceptor sites, from a starting arylboronic acid is described.