Sequential two-electron transfer from tetraoxy-substituted cyclopropane to acceptors [2]

Journal of the American Chemical Society

Volumn 122, Issue 30, 2000, Pages 7388-7389

  Oku, Akira ^a   Takahashi, Hirosato ^a   Asmus, Sven M ^a  

^a KYOTO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZOPHENONE; CYCLOPROPANE;

CHEMICAL REACTION; CHEMICAL STRUCTURE; ELECTRON TRANSPORT; LETTER; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STOICHIOMETRY; STRUCTURE ANALYSIS;

EID: 0034596335     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992397g     Document Type: Letter

References (26)

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8. Fukuzumi, S.; Fujita, M., Otera, J.; Fujita, Y. J. Am. Chem. Soc. 1992, 114, 10271.
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10. (a) Abe, M.; Oku, A. J. Chem. Soc., Chem. Commun. 1994, 1673.
11. (b) Abe, M.; Oku, A. J. Org. Chem. 1995, 60, 3065.
12. MOPAC PM3 calculation showed that the HOMO energy (-IP) of phenylcyclopropane (-9.46 eV) is higher than those of benzene (-9.74) and cyclopropane (-11.75), and the electrons are mainly distributed on the phenyl group.
13. 3-cyclopropanes showed a remarkable difference in IPs, i.e., 10.33 and 8.86 eV.
14. 1H NMR measurement of the reaction mixture of TCNE and 1 (a 33:67 mixture of cis and trans isomers) showed the formation of cycloadducts with a different isomer ratio (15:85).The observed nonstereospecificity indicates that the reaction is stepwise rather than concerted. The cycloadducts, however, were too labile to be isolated and only one product (malonate 4) was identified. Similar cycloadducts were reported to be isolable (ref 5b) for the reaction of CPA (ref 9) with TCNE.
15. To determine the relative reactivity of 1 vs 1-MeO-1-OTMS-2-Ph-cyclopropane (CPA) (see refs 5a,b), a mixture of 1 and CPA was treated with DDQ to produce 4 (6.3%), methyl 3-phenylpropenoate (54%), 5 (X = CN, Y = H, 100%), and recovered 1 (43%) but no CPA. This indicates that CPA, which has a phenyl group, reacts much faster than 1.
16. See Oku, A.; Abe, M.; Iwamoto, M. J. Org. Chem. 1994, 59, 7445: the formation of both C-C and C-O bonded intermediates was reported in the reaction of DDQ or CA with CPA (ref 9).
17. 4.
18. This type of two-electron transfer was observed with other aryl ketones, e.g., acetophenone, 1,4-diacetylbenzene and 4-cyanoacetophenone.
19. 2 improves the quantum yield of electron transfer: see (a) Fukuzumi, S.; Okamoto, T. J. Am. Chem. Soc. 1994, 116, 5503. (b) Mizuno, K.; Ichinose, N.; Otsuji, Y. J. Org. Chem. 1992, 57, 1855.
20. 2 improves the quantum yield of electron transfer: see (a) Fukuzumi, S.; Okamoto, T. J. Am. Chem. Soc. 1994, 116, 5503. (b) Mizuno, K.; Ichinose, N.; Otsuji, Y. J. Org. Chem. 1992, 57, 1855.
21. The yield of pinacol was calculated on the molar basis of 1.
22. We presume that the SET takes place more efficiently with complexed ketones than uncomplexed ones.
23. Measurement and Estimation of Redox Potentials of Organic Radicals. In General Aspects of the Chemistry of Radicals; Alfassi, Z. B., Ed.; Wiley & Sons: New York, 1999; Chapter 12, Table 2, pp 419-422.
24. Calculated MO-energy levels of 16 (MeO analogue) are -8.9 (HF631G*), -8.7 (HF321G*) and -8.4 eV (PM3), being higher by 1 eV than those of 1 (MeO analogue) -9.8, -9.9, and -9.2 eV, respectively.
25. Additional photon is required for this process.
26. Pitts, J. N.; Letsinger, R. L.; Taylor, R. P.; Patterson, J. M.; Recktenwald, G.; Martin, R. B. J. Am. Chem. Soc. 1959, 81, 1068.