First example of an enone-alkene [2 + 2 + 2] photocycloaddition: 1,3-photocycloaddition of tetramethylethylene across 2,7-cyclooctadienone

Organic Letters

Volumn 1, Issue 2, 1999, Pages 303-305

  Matlin, Albert R ^a   Lin, Susanne C ^a   Patel, Hiren R ^a   Chai, Minghui ^b  

^a OBERLIN COLLEGE   (United States)

^b UNIVERSITY OF AKRON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000704672     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol990055+     Document Type: Article

References (24)

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7. Becker, D.; Haddad, N. In Organic Photochemistry; Padwa, A., Ed.; Marcel Dekker: New York, 1989; Vol. 10; pp 1-162.
8. Gilbert, A.; Baggott, J. Essentials of Molecular Photochemistry; Blackwell Scientific Publishing: London, 1991; pp 340-352.
9. Matlin, A. R.; Jin, K. Tetrahedron Lett. 1989, 30, 637-640.
10. Matlin, A. R.; Lahti, P. M.; Appella, D.; Straumanis, A.; Lin, S.; Patel, H.; Jin, K.; Schreiber, K. P.; Pauls, J.; Raulerson, P. J. Am. Chem. Soc. 1999, 121, 2164-2173.
11. No 1:1 adducts were observed when 1 was irradiated in the presence of electron-deficient π-systems such as 1,2-dichloroethylene and dimethyl acetylenedicarboxylate. See: Haseltine, R. P. Ph.D. Thesis, University of Indiana, 1970.
12. Rahman, A. Nuclear Magnetic Resonance; Spring-Verlag: New York, 1986; pp 79, 182-184.
13. The reaction of TME with 8 requires a front-side attack with respect to the cleaving C-O bond. Examination of the LUMO in 8 (geometry-optimized structure, 3-21G*) shows a substantial π antibonding interaction between the bridgehead methine carbon and oxygen. Only the "front-side" lobe of the orbital on the bridgehead methine is sterically accessible for reaction with TME.
14. Dodziuk, H.; Leszczynski, J. Pol. J. Chem. 1998, 72, 2030-2033.
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19. Branan, B. M.; Wang, X.; Jankowski, P.; Wicha, J.; Paquette, L. A. J. Org. Chem. 1994, 59, 6874-6876.
20. Concerted retro-cycloaddition of 8 should produce 2. For a discussion on the stereochemistry of retro-cycloadditions in bicyclobutanes, see: Woodward, R. B.; Hoffmann, R. In The Conservation of Orbital Symmetry; Academic Press: Germany, 1971; pp 75-78.
21. Chapman, O. L.; Adam, W. R. J. Am. Chem. Soc. 1968, 90, 2333-2342.
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24. Structures derived from DFT-MO calculations (see ref 9) indicate that the distance between the carbonyl and β-enone carbons is 2.609 Å in 1 and 2.429 Å in 2 (from β-carbon in trans double bond).