Journal
DALTON TRANSACTIONS
Volume 42, Issue 12, Pages 4175-4184Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3dt31898b
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Funding
- NSFC [21272223, 21202006]
- SRFDP [20123402110051]
- FRFCU [WK2060190008]
- CAS [KJCX2-EW-J02]
- Shenzhen municipality [JC201005260104A]
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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 sigma-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 beta-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.
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