Photodissociation of the Product from a Transition-Metal Center Allows the Catalytic Cycle to Proceed: The Rhodium(I)-Catalyzed [2+2+1] Carbonylative Cycloaddition of Diynes

JingWen Jia; Tsumoru Morimoto; Yoshiko Yamaguchi; Hiroki Tanimoto; Kiyomi Kakiuchi

doi:10.1021/acs.orglett.1c01631

Photodissociation of the Product from a Transition-Metal Center Allows the Catalytic Cycle to Proceed: The Rhodium(I)-Catalyzed [2+2+1] Carbonylative Cycloaddition of Diynes

Org Lett. 2021 Jun 18;23(12):4893-4897. doi: 10.1021/acs.orglett.1c01631. Epub 2021 Jun 9.

Authors

JingWen Jia¹, Tsumoru Morimoto¹, Yoshiko Yamaguchi¹, Hiroki Tanimoto², Kiyomi Kakiuchi¹

Affiliations

¹ Division of Materials Science, Nara Institute of Science and Technology (NAIST), Ikoma, Nara 630-0192, Japan.
² Academic Assembly, Faculty of Pharmaceutical Sciences, University of Toyama, 2630 Sugitani, Toyama 930-0194, Japan.

PMID: 34105976
DOI: 10.1021/acs.orglett.1c01631

Abstract

We describe the effective rhodium(I)-catalyzed [2+2+1] carbonylative cycloaddition of diynes, yielding cyclopentadienes (CPDs), under photoirradiation. The catalysis involves the promotion of the photodissociation of the product CPD, with the simultaneous production of an essential vacant coordination site on the rhodium for an unreacted substrate. The combined use of cationic [Rh(cod)₂]BF₄ as a catalyst and photoirradiation was also found to give various CPDs in high yields (≤96%).