Mechanistic Support for Intramolecular Migrative Cyclization of Propargyl Sulfones Provided by Catalytic Asymmetric Induction with a Chiral Counter Cation Strategy. Issue 7 (10th May 2021)

• Record Type: Journal Article
• Authors: Yamasaki, Kohta; Yamauchi, Akiho; Inokuma, Tsubasa; Miyakawa, Yasunori; Wang, Yinli; Oriez, Raphaël; Yamaoka, Yousuke; Takasu, Kiyosei; Tanaka, Naonobu; Kashiwada, Yoshiki; Yamada, Ken‐ichi
• Is Part Of: Asian journal of organic chemistry. Volume 10:Issue 7(2021)
• Page Start: 1828
• Page End: 1834
• Publication Date: 2021-05-10
• Subjects: sulfonyl migration -- cyclization -- organocatalyst -- asymmetric reaction -- catalytic reaction; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.202100274
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: We previously reported an intramolecular migrative cyclization of propargylsufones and sulfonylalkynamides giving oxa‐ and azacycles, respectively. To confirm the postulated reaction mechanism, the reaction was conducted with chiral nucleophiles such as N‐heterocyclic carbenes, phosphines, and pyridines, or with sulfinate anions and chiral cations. As expected, migrative cyclization proceeded to give the enantiomerically enriched products. These results strongly support the postulated mechanism and provide the first example of the asymmetric version of this reaction. Abstract : To confirm the postulated reaction mechanism of sulfonylalkynols and sulfonylalkynamides, reactions of these compounds were conducted with chiral nucleophiles such as N‐heterocyclic carbenes, phosphines, and pyridines, or with sulfinate anions and chiral cations. As expected, migrative cyclization proceeded to give the enantiomerically enriched products. These results strongly support the postulated mechanism and provide the first example of the asymmetric version of this reaction.