Gram‐Scale Synthesis of β‐(Hetero)arylethenesulfonyl Fluorides via a Pd(OAc)2 Catalyzed Oxidative Heck Process with DDQ or AgNO3 as an Oxidant. Issue 18 (25th July 2017)

• Record Type: Journal Article
• Authors: Zha, Gao‐Feng; Bare, Grant A. L.; Leng, Jing; Shang, Zhen‐Peng; Luo, Zhixiong; Qin, Hua‐Li
• Is Part Of: Advanced synthesis & catalysis. Volume 359:Issue 18(2017)
• Page Start: 3237
• Page End: 3242
• Publication Date: 2017-07-25
• Subjects: Arylethenesulfonyl fuorides -- Oxidative Heck reaction -- Sulfur(VI) fluoride exchange -- Palladium catalyst; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201700688
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: 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 AgNO3 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. Abstract :