期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 86, 期 17, 页码 12046-12053出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.joc.1c01410
关键词
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资金
- JSPS KAKENHI [17F17340, 17H03022, 20K21197]
- Grants-in-Aid for Scientific Research [17F17340, 17H03022, 20K21197] Funding Source: KAKEN
Photolysis of AZ1 and AZ2 derivatives resulted in the formation of singlet cyclopentane-1,3-diyl diradicals with distinct structural characteristics, which were detected and characterized using infrared and UV-vis spectroscopy. This method provides a new strategy for obtaining detailed information about the structure and reactivity of these diradicals.
Photolysis of a 7,7-difluoro-1,4-diphenyl-2,3-diazabicyclo[2.2.1]hept-2-ene derivative (AZ1) using a 365 nm light-emitting diode in an Ar matrix at 4 K resulted in the formation of a planar singlet 2,2-difluoro-1,3-diphenylcyclopentane-1,3-diyl diradical derivative, S-DR1-pl (lambda(max) = 520 nm). A singlet cyclopentane-1,3-diyl diradical system (S-DR1-pl) was directly detected by steady-state infrared (IR) spectroscopy. Due to the photolability of S-DR1-pl, initial photolysis of AZ1 also yielded the ring-closed product ret-CP1 and migration products trans-MG1 and/or cis-MG1, which were observed using IR spectra. Monitoring of prolonged photolysis using IR and ultraviolet-visible (UV-vis) spectra demonstrated the formation of the allylic cation CT1 (lambda(max) = 470 nm). On the other hand, photolysis of a 7,7-dimethoxy-1,4-diphenyl-2,3-diazabicyclo[2.2.1]hept-2-ene derivative (AZ2) yielded a puckered conformer (instead of planar) of the corresponding diradical S-DR2-puc, which was detected by IR and UV-vis spectroscopy in an Ar matrix at 4 K. This spectroscopic characterization opens a new strategy to obtain more detailed information about the structure and reactivity of singlet cyclopentane-1,3-diyl diradicals.
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