Rhodium‐Catalyzed Cross‐Cyclotrimerization and Dimerization of Allenes with Alkynes. Issue 23 (25th April 2016)

• Record Type: Journal Article
• Authors: Sakashita, Kazuki; Shibata, Yu; Tanaka, Ken
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 23(2016)
• Page Start: 6753
• Page End: 6757
• Publication Date: 2016-04-25
• Subjects: alkynes -- allenes -- cyclization -- dimerization -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201602155
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: It has been established that a cationic rhodium(I)/binap complex catalyzes the cross‐cyclotrimerization of two molecules of a monosubstituted allene with one molecule of a functionalized alkyne to give 3, 6‐dialkylidenecyclohex‐1‐enes. In contrast, the reactions involving di‐ or trisubstituted allenes and/or unfunctionalized alkynes afforded cross‐dimerization products, substituted dendralenes, through β‐hydrogen elimination from the corresponding rhodacycles. Abstract : A triple cross : A cationic rhodium(I)/binap complex catalyzes the cross‐cyclotrimerization of two molecules of a monosubstituted allene with one molecule of a functionalized alkyne to give 3, 6‐dialkylidenecyclohex‐1‐enes. In contrast, the reactions involving di‐ or trisubstituted allenes and/or unfunctionalized alkynes afforded cross‐dimerization products, substituted dendralenes. binap=2, 2′‐bis(diphenylphosphino)‐1, 1′‐binaphthyl.