Palladium(0)-Catalyzed Regioselective Synthesis of Macrocycles from Allenes with a Nucleophilic Functionality and Organic Iodides

• Published in: Advanced synthesis & catalysis Vol. 355; no. 16; pp. 3295 - 3303
• Main Authors: Huang, Xin, Jiang, Xinpeng, Fu, Chunling, Ma, Shengming
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 11.11.2013; WILEY‐VCH Verlag; Wiley
• Subjects: Allene; allenes; Bearing; Carbon; carbopalladation; Catalysis; Chemistry; Chemistry, Applied; Chemistry, Organic; cyclization; Iodides; Joining; macrocycles; Macrocyclic compounds; Physical Sciences; Science & Technology; Synthesis; Terminals; MULTIPLE MULTICOMPONENT MACROCYCLIZATIONS; ASYMMETRIC-SYNTHESIS; NATURAL-PRODUCTS; COMPLEXES; carbopalladation; cyclization; STRATEGIES; allenes; macrocycles; BIOSYNTHESIS; BIOLOGICAL EVALUATION; CATALYZED CYCLIZATION; STEREOSELECTIVE-SYNTHESIS; METATHESIS
• ISSN: 1615-4150; 1615-4169
• DOI: 10.1002/adsc.201300602

A highly regioselective synthesis of 15–20‐membered macrocycles via Pd(0)‐catalyzed coupling cyclization of allenes bearing a carbon or nitrogen nucleophilic functionality and organic iodides is reported. After oxidative addition and carbopalladation, anti‐π‐allyl palladium intermediates were formed, which was followed by the exclusive intramolecular nucleophilic attack at the terminal carbon atom of the allene moiety to afford products with yields ranging from 44–92% and E/Z ratios of up to 97/3.