First Stereoselective Total Synthesis and Biological Evaluation of Amphidinin B and Its Analogues

• Published in: European Journal of Organic Chemistry Vol. 2011; no. 4; pp. 696 - 706
• Main Authors: Yadav, Jhillu S., Reddy, A. Srinivas, Reddy, Ch. Suresh, Reddy, Basi V. Subba, Saddanapu, Venkateshwarlu, Addlagatta, Anthony
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.02.2011; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Chemistry; Chemistry, Organic; Chemoselectivity; Diastereoselectivity; Enzyme catalysis; Exact sciences and technology; Free radicals chemistry; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Macrocycles; Natural products; Organic chemistry; Oxidation; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Total synthesis; Enzyme catalysis; Natural products; Chemoselectivity; DINOFLAGELLATE; FRAGMENT; Oxidation; Macrocycles; MACROLIDES; Total synthesis; Diastereoselectivity; One pot reaction; Sharpless epoxidation; Furan derivatives; Oxygen heterocycle; Ring cleavage; Allylation; Macrocycle; Chemical reduction; Stereoselectivity; Asymmetric synthesis; Yamaguchi esterification; Debenzylation; Catalysis; Chemical synthesis; Catalytic reaction; Enzyme; Exo stereoisomer; Natural compound; Biological activity; Cyclization; Cyclic compound; Optical resolution; Organic free radical; Epoxide; Kinetic resolution; Ethylenic compound
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201001205

A highly stereoselective first total synthesis of amphidinin B is described. The key steps involved in this synthesis are the generation of the exo‐double bond in the C1–C9 segment, the Barbier allylation, enzymatic kinetic resolution, and the construction of the C10–C21 segment by Sharpless asymmetric epoxidation, base‐induced epoxide ring‐opening, radical cyclization, diastereoselective reduction of the exo‐cyclic double bond, one‐pot allylation followed by debenzylation, Evans alkylation, and Yamaguchi esterification. The first stereoselective synthesis of amphidinin B has been achieved following Sharpless asymmetric epoxidation, base‐induced epoxide ring‐opening, radical cyclization, diastereoselective reduction of the exo‐cyclic double bond, one‐pot allylation followed by debenzylation, Evans alkylation, Barbier allylation, enzymatic kinetic resolution, and Yamaguchi esterification.