Cationic Rhodium(I)‐Catalyzed Carbonylative [2+2+1] Cycloaddition of Diynes. Issue 11 (7th October 2020)

• Record Type: Journal Article
• Authors: Morimoto, Tsumoru; Jia, JingWen; Yamaguchi, Yoshiko; Tanimoto, Hiroki; Kakiuchi, Kiyomi
• Is Part Of: Asian journal of organic chemistry. Volume 9:Issue 11(2020)
• Page Start: 1778
• Page End: 1782
• Publication Date: 2020-10-07
• Subjects: [2+2+1] cycloaddition -- rhodium -- carbon monoxide -- diynes -- cyclopentadienones; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; 547.005
• DOI: 10.1002/ajoc.202000436
• Languages: English
• ISSNs: 2193-5807

Abstract

Abstract: We describe Rh(I)‐catalyzed carbonylative [2+2+1] cycloaddition reactions of diynes with CO to give cyclopentadienone derivatives (CPDs). Previous reports on the use of neutral rhodium(I) complexes, such as [RhCl(cod)]2 and RhCl(PPh3 )3, indicate that no CPD products are formed or that they are produced in low yields, even at elevated temperatures. The reaction described herein, which uses a cationic rhodium(I) complex, [Rh(cod)2 ]BF4, as a catalyst, proceeds smoothly at room temperature to give cyclopentadienone derivatives. The key to this is the use the cationic rhodium(I) complex as a catalyst, which produces an additional coordination site on the rhodium for the substrate (a diyne) to approach, than neutral rhodium complexes. Abstract : A cationic rhodium(I) complex, [Rh(cod)2 ]BF4, catalyzes carbonylative [2+2+1] cycloaddition reactions of diynes with CO at room temperature to give cyclopentadienone derivatives.