期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 123, 期 4, 页码 958-965出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.8b10290
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资金
- U.S. Department of Energy, Office of Basic Energy Sciences (Chemical Sciences, Geosciences and Biosciences Division) [DE-FG02-03ER15387]
- National Science Foundation [CHE-1531468]
Anti-Markovnikov addition of water to olefins has been a long-standing goal in catalysis. The [Rh(COD)(DPEphos)](+) complex was found as a general and regioselective group 9 catalyst for intermolecular hydroamination of alkenes. The reaction mechanism was adapted for intermolecular hydration of alkenes catalyzed by a [Rh(DPEphos)](+) catalyst and studied by DFT calculations. Olefin hydration pathways were analyzed for anti-Markovnikov and Markovnikov regioselectivity. On the basis of the DFT results, the operating mechanism can be summarized as follows: styrene activation through nucleophilic attack by OH delta- of water to alkene with simultaneous H delta+ transfer to the Rh; this is then followed by formation of primary alcohol via reductive elimination. The competitive formation of phenylethane was studied via a beta-elimination pathway followed by hydrogenation. The origin of the regioselectivity (Markovnikov vs anti-Markovnikov) was analyzed by means of studying the molecular orbitals, plus natural atomic charges, and shown to be primarily orbital-driven rather than charge-driven.
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