Mechanistic Insights Into the Rhodium-Catalyzed C-H Alkenylation/Directing Group Migration and [3+2] Annulation: A DFT Study.
J Org Chem
; 88(7): 4494-4503, 2023 Apr 07.
Article
in En
| MEDLINE
| ID: mdl-36972416
ABSTRACT
The mechanism of the rhodium-catalyzed C-H alkenylation/directing group migration and [3+2] annulation of N-aminocarbonylindoles 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 ß-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.
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Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
J Org Chem
Year:
2023
Document type:
Article