Synthesis of Enantiopure tert-Butanesulfinamide from tert-Butanesulfinyloxazolidinone

• Published in: Journal of organic chemistry Vol. 69; no. 24; pp. 8533 - 8536
• Main Authors: Qin, Yong, Wang, Canhui, Huang, Zhiyan, Xiao, Xue, Jiang, Yaozhong
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 26.11.2004; Amer Chemical Soc
• Subjects: Chemistry; Chemistry, Organic; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with n hetero atom and also o and/or s, se, te hetero atoms; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; BUTYL DISULFIDE; OXIDATION; CATALYSIS; ASYMMETRIC-SYNTHESIS; BIS(SULFINYL)IMIDOAMIDINE LIGANDS; SYN-1,3-AMINO; AMINES; ANTI-1,3-AMINO ALCOHOLS; UTILITY; IMINE LIGANDS; Organic synthesis; Chemical rearrangement; Five membered ring; Catalytic reaction; Base catalysis; Enantioselectivity; Asymmetric synthesis; Oxazolidinone derivative; Oxygen nitrogen heterocycle
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo048576k

A three-step procedure for the preparation of enantiopure tert-butanesulfinamide 6 in 51% overall yield is described starting from (1R,2S)-N-Cbz-1,2-diphenylaminoethanol. The key step is the reaction of tert-butylmagnesium chloride with N-Cbz-4,5-diphenyl-1,2,3-oxathiazolidine-2-oxide 2 to afford the optical pure tert-butylsulfinyl-4,5-diphenyl-1,3-oxazolidinone 5 via an 1,5-alkoxy anion rearrangement, which is then subject to ammonia hydrolysis with LiNH2 in liquid ammonia to give (R)-tert-butanesulfinamide 6.