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- W2040694793 abstract "The mechanisms and enantioselectivities of the dirhodium (Rh2L4, 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)." @default.
- W2040694793 created "2016-06-24" @default.
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- W2040694793 date "2013-12-05" @default.
- W2040694793 modified "2023-10-04" @default.
- W2040694793 title "Mechanism and Enantioselectivity of Dirhodium-Catalyzed Intramolecular C–H Amination of Sulfamate" @default.
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- W2040694793 doi "https://doi.org/10.1021/jo402101h" @default.
- W2040694793 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/24308708" @default.
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