Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 25, Pages 9271-9274Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja4036785
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Funding
- NSF [CHE-1059084]
- NIH [R01GM088285]
- Natural Science Foundation of China [21103094]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1059084] Funding Source: National Science Foundation
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The mechanism of Rh-catalyzed (5+2) cycloadditions of 3-acyloxy-1,4-enyne (ACE) and alkynes is investigated using density functional theory calculations. The catalytic cycle involves 1,2-acyloxy migration, alkyne insertion, and reductive elimination to form the cycloheptatriene product. In contrast to the (5+2) cycloadditions with vinylcyclopropanes (VCPs), in which alkyne inserts into a rhodium-allyl bond, alkyne insertion into a Rh-C(sp(2)) bond is preferred. The 1,2-acyloxy migration is found to be the rate-determining step of the catalytic cycle. The electron-rich p-dimethylaminobenzoate substrate promotes 1,2-acyloxy migration and significantly increases the reactivity. In the regioselectivity-determining alkyne insertion step, the alkyne substituent prefers to be distal to the forming C-C bond and thus distal to the OAc group in the product.
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