US EPA

5068507 

Journal Article 

Direct Anti-Markovnikov Addition of Water to Olefin To Synthesize Primary Alcohols: A Theoretical Study 

Ceylan, YS; Cundari, TR 

2019 

1 

Journal of Physical Chemistry A
ISSN: 1089-5639
EISSN: 1520-5215 

123 

4 

958-965 

English 

30615443 

10.1021/acs.jpca.8b10290 

WOS:000457816100023 

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85060904473&doi=10.1021%2facs.jpca.8b10290&partnerID=40&md5=54afea19728cc6697e5b1ea95febdbb6
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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 OHδ- of water to alkene with simultaneous Hδ+ 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 β-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.