Dimethyl amino[(phenylthio)methyl]malonate: a useful C-3 unit in a mild, direct synthesis of oxazole-4-carboxylates

• Published in: Journal of organic chemistry Vol. 58; no. 21; pp. 5759 - 5764
• Main Author: Shapiro, Rafael
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 01.10.1993; 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; CALYCULIN-A; HYDROLYSIS; FRAGMENT; OXAZOLE; LACTAMS; ACID; Five membered ring; Aminoester; Cyclization; Diester; Carboxamide; Oxidation; Oxygen nitrogen heterocycle
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo00073a040

N-Acyl derivatives of the title compound undergo oxidative cyclization upon treatment with N-chlorosuccinimide in DMF to form dimethyl 4,5-dihydro(phenylthio)oxazole-4,4-dicarboxylates 4 which then are decarbomethoxylated with concomitant loss of thiophenoxide to form 2-substituted-4-carbomethoxy-5-unsubstituted oxazoles 1. The mildness and generality of this method has been demonstrated by the synthesis of a variety of examples, including a fragment used for a synthesis of calyculin A.