Asymmetric Synthesis of Protected Cyclohexenylamines and Cyclohexenols by Rhodium‐Catalyzed [2+2+2] Cycloaddition. Issue 49 (10th November 2016)

• Record Type: Journal Article
• Authors: Masutomi, Koji; Sugiyama, Haruki; Uekusa, Hidehiro; Shibata, Yu; Tanaka, Ken
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 49(2016)
• Page Start: 15373
• Page End: 15376
• Publication Date: 2016-11-10
• Subjects: asymmetric catalysis -- cycloadditions -- enamides -- reaction mechanisms -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201608952
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1, 6‐enynes with electron‐rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Interestingly, regioselectivity depends on structures of substrates. The present cycloaddition was successfully applied to the enantioselective total synthesis of (−)‐porosadienone by using the amide moiety as a leaving group. Abstract : 2+2+2=6 : It has been established that cationic rhodium(I)/axially chiral biaryl bis(phosphine) complexes catalyze the asymmetric [2+2+2] cycloaddition of 1, 6‐enynes with electron‐rich functionalized alkenes, enamides, and vinyl carboxylates, to produce the corresponding protected cyclohexenylamines and cyclohexenols. Regioselectivity depends on structures of substrates. The present cycloaddition was used in the enantioselective total synthesis of (−)‐porosadienone.