title: Reaction mechanism and stereoselectivity of ruthenium--porphyrin-catalyzed intramolecular amidation of sulfamate ester: a DFT computational study.
abstract: The reaction mechanism of the ruthenium--porhyrin complex [Ru(por)(CO)]-catalyzed intramolecular C-H bond amidation was examined using density functional theory (DFT) calculations. The metal-nitrene reactive intermediate, Ru(por)(CO)-NSO3R1 (R1 = 1-methylclohexl-methyl) was found to be highly favorable to generate in terms of the free energy profile from the reaction of the starting materials. Ru(por)(CO)-NSO3R1 may exist in both singlet and triplet states since they are close in energy. In each state, six C-H bond amidation reaction pathways were characterized structurally and energetically. The predicted most probable diastereomeric product out of the four possible diasteromeric products examined in the calculations for the amidation reactions agree well with previously reported experimental results.
authors: Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong, PR 11111, China.
authors: Xufeng
authors: X
authors: Lin
authors: Chi-Ming
authors: CM
authors: Che
authors: David Lee
authors: DL
authors: Phillips
mesh_terms: D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D004952:Esters / Q000737:chemistry*; D008956:Models, Chemical; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011166:Porphyrins / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry; D013237:Stereoisomerism; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D000577:Amides; D004952:Esters; D009942:Organometallic Compounds; D011166:Porphyrins; D013451:Sulfonic Acids; D012428:Ruthenium; C005741:sulfamic acid