81. Mechanistic Insights Into the Rhodium-Catalyzed C−H Alkenylation/ Directing Group Migration and [3+2] Annulation: A DFT Study

Ling, B.;* Wang, S.; Xie, Y.; Liu, P.; Jiang, Y.-Y.; Zhong, W.; Bi, S.* J. Org. Chem. 2023, 88, 4494-4503. Download Link.

Abstract: The mechanism of the rhodium-catalyzed C−H alkenylation/directing group migration and [3+2] annulation of Naminocarbonylindoles with 1,3-diynes has been investigated with DFT calculations. On the basis of mechanistic studies, we mainly focus on the regioselectivity of 1,3-diyne inserting into the Rh−C bond and the N-aminocarbonyl directing group migration involved in the reactions. Our theoretical study uncovers that the directing group migration undergoes a stepwise β-N elimination and isocyanate reinsertion process. As studied in this work, this finding is also applicable to other relevant reactions. Additionally, the role of Na+ versus Cs+ involved in the [3+2] cyclization reaction is also probed.