45. Theoretical study on the intramolecular oxyamination involved in Rh(III)-catalyzed cyclization of unsaturated alkoxyamines

Bi, S.;* Wang, Y.; Jiang, Y.-Y.; Liu, Y. J. Organomet. Chem. 2019, 880, 253–256. Download Link

Abstract: The unexpected oxyamination reaction of O, u-unsaturated alkoxyamines was found experimentally. The mechanistic issues were studied by DFT calculations. It is suggested that the reaction undergoes [3 þ 2] cyclic addition, OeN bond cleavage, CeN reductive elimination, and the RheN unit protonation, generating the product and regenerating the active catalyst. The nitrene Rh(V) species containing a RheC bond rather than a RheO bond was suggested to be involved in the reaction mechanism. Why the substrate A with X ¼ O but not X ¼ C undergoes oxyamination reaction was rationalized based on the suggested reaction mechanism.