期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 77, 期 17, 页码 7612-7619出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo3016105
关键词
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资金
- Tolcuyama Science Foundation
- Mazda Foundation
- Natural Sciences and Engineering Research Council (NSERC) of Canada
- [24109008]
- [21108516]
- [19350021]
- Grants-in-Aid for Scientific Research [24109008] Funding Source: KAKEN
Stretch effects induced by two types of molecular strain were examined by quantum chemical calculations at the B3LYP/6-31G(d), B3LYP/cc-PVDZ, CCSD/6-31G(d), and CASPT2/ANO-RCC-VTZP level of theory, to design persistent multiradicals such as localized diradicals and oxyallyls. The cooperative molecular strain (Type-1) induced by the spiro[5.5]-undecane and bicydo[2.1.0]cyclopentane structures was found to significantly destabilize in energy the ring-closed compounds of the diraclicals, leading to small energy differences between the diradicals and the a-bonded compounds. Another stretch effect (Type-2) induced by macrocyclic systems was also found to energetically destabilize the corresponding ring-closed structures of the 1,3-diradicals. The computational studies predict that the two types of stretch effects are quite effective in lowering the energy barriers of the bond-breaking reaction of the ring-closed compounds and in generating long-lived localized diradicals and oxyallyl derivatives.
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