期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 82, 期 4, 页码 2150-2159出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.6b02957
关键词
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资金
- MEXT (Ministry of Education Culture, Sports, Science and Technology in Japan) program Elements Strategy Initiative to Form Core Research Center
- Grants-in-Aid for Scientific Research [16H06511, 16H04104] Funding Source: KAKEN
The reaction mechanism and origins of ligand-controlled selectivity, regioselectivity, and stereoselectivity of Ni-catalyzed (2 + 2 + 2) cycloadditions and alkenylative cyclizations of 1,6-ene-allenes and alkenes were studied by using density functional theory. The catalytic cycle involves intermolecular oxidative coupling and an intramolecular concerted 1,4-addition step to afford a stable metallacycloheptane intermediate; these steps determine both the regioselectivity and stereoselectivity. Subsequent C-C reductive elimination leads to the cyclohexane product, whereas the beta-hydride elimination leads to the trans-diene product. The selectivity between (2 + 2 + 2) cycloadditions and alkenylative cyclizations is controlled by the ligand. Irrespective of the nature of the terminal substituents on the ene allene and alkene, the P(o-tol)(3) ligand always favors the C-C reductive elimination, resulting in the cydohexane product. On the other hand, the flexibility of the PBu3 ligand means that electronic and steric factors play important roles. Electron-withdrawing groups such as CO2Me in the ene allene terminal substituent induce obvious substrate ligand repulsion and destabilize the C-C reductive elimination, giving rise to the trans-diene product.
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