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Issue 12, 2013
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Computational study on mechanism of Rh(iii)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes

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Abstract

A systematic theoretical study on the Rh-catalyzed oxidative Heck-coupling of phenol carbamates with alkenes is carried out. Two possible mechanisms (i.e. arene activation-first and alkene activation-first mechanisms) are examined. As to the C–H activation step, four mechanisms including oxidative addition, electrophilic substitution, concerted metallation-deprotonation (CMD), and σ-bond metathesis are evaluated. The calculation results indicate that the arene activation-first mechanism is more favorable for the overall catalytic cycle. This mechanism involves three steps: arene C–H activation at the position ortho to the carbamate directing group affording a six-membered rhodiacycle intermediate, insertion of the alkene double bond into the Rh(III)–aryl bond, and a final β-H elimination step to release the product and re-generate the catalyst. The rate determining step of the overall catalytic cycle is the arene C–H activation step, which is found to proceed through the acetate-assisted CMD mechanism.

Graphical abstract: Computational study on mechanism of Rh(iii)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes

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Publication details

The article was received on 18 Aug 2012, accepted on 07 Jan 2013 and first published on 06 Feb 2013


Article type: Paper
DOI: 10.1039/C3DT31898B
Dalton Trans., 2013,42, 4175-4184

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    Computational study on mechanism of Rh(III)-catalyzed oxidative Heck coupling of phenol carbamates with alkenes

    Q. Zhang, H. Yu, Y. Li, L. Liu, Y. Huang and Y. Fu, Dalton Trans., 2013, 42, 4175
    DOI: 10.1039/C3DT31898B

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