Mechanism and enantioselectivity of dirhodium-catalyzed intramolecular C-H amination of sulfamate


The mechanisms and enantioselectivities of the dirhodium (Rh 2L4, L = formate, N-methylformamide, S-nap)-catalyzed intramolecular C-H aminations of 3-phenylpropylsulfamate ester have been investigated in detail with BPW91 density functional theory computations. The reactions catalyzed by the Rh2II,II catalysts start from the oxidation of the Rh2II,II dimer to a triplet mixed-valent Rh2II,III-nitrene radical, which should facilitate radical H-atom abstraction. However, in the Rh2(formate) 4-promoted reaction, as a result of a minimum-energy crossing point (MECP) between the singlet and triplet profiles, a direct C-H bond insertion is postulated. The Rh2(N-methylformamide)4 reaction exhibits quite different mechanistic characteristics, taking place via a two-step process involving (i) intramolecular H-abstraction on the triplet profile to generate a diradical intermediate and (ii) C-N formation by intersystem crossing from the triplet state to the open-shell singlet state. The stepwise mechanism was found to hold also in the reaction of 3-phenylpropylsulfamate ester catalyzed by Rh2(S-nap)4. Furthermore, the diradical intermediate also constitutes the starting point for competition steps involving enantioselectivity, which is determined by the C-N formation open-shell singlet transition state. This mechanistic proposal is supported by the calculated enantiomeric excess (94.2% ee) with the absolute stereochemistry of the product as R, in good agreement with the experimental results (92.0% ee). © 2013 American Chemical Society.

Publication Title

Journal of Organic Chemistry