[3+2] versus [4+3] cycloaddition of conjugated dienes to TMM diradicals

Tetrahedron Letters

Volumn 43, Issue 47, 2002, Pages 8459-8461

  Russu, Wade A ^a   Villalon, Veronica P ^a   Wang, Vivian R ^a   Miranda, James A ^a   Little, R Daniel ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Sigmatropic rearrangement; TMM diradicals; 3+2 and 4+3 cycloaddition reactions

Indexed keywords

ALKADIENE; METHANE; RADICAL; TRIMETHYLENEMETHANE; UNCLASSIFIED DRUG;

ARTICLE; CONJUGATION; CYCLOADDITION; ENERGY; ISOMER; PYROLYSIS;

EID: 0037131707     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(02)02098-1     Document Type: Article

References (16)

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6. (a) Siemionko, R.; Shaw, A.; O'Connell, G.; Little, R. D.; Carpenter, B. K.; Shen, L.; Berson, J. A. Tetrahedron Lett. 1978, 3529-3532. See also: (b) Lazzara, M. G.; Harrison, J. J.; Rule, M.; Hilinski, E. F.; Berson, J. A. J. Am. Chem. Soc. 1982, 104, 2233-2243.
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11. As the ratio of diylophile to diazene decreases from 10:1 to 3:1 to 1:1, the amount of diyl dimerization increases.
12. 13C NMR (100 MHz) δ 28.2, 29.2, 29.4, 33.4, 51.3, 119.7, 123.5, 124.7, 125.5, 125.7, 125.2, 126.6, 126.7, 127.3, 127.8, 127.9.
13. For an overview of the route used to synthesize diazenes like 13, see: Little R.D. Chem. Rev. 96:1996;93-114.
14. 3). For 14: δ 7.00 (dd, 1H, J=8, 16 Hz), 6.73 (dd, 1H, J=8, 16), 5.74 (d, 1H, J=16 Hz), 5.28 (br m, 1H), 3.72 (s, methyl), 3.32 (m, 1H); alkane region 2.87 (m, 2H), 2.54 (m, 4H), 1.92 (m, 2H), 1.64 (m, 2H), 1.39 (m, 2H). For 15: δ 7.06 (dd, 1H, J=8, 16 Hz), 6.98 (dd, 1H, J=8, 16 Hz), 5.80 (d, 1H, J=16 Hz), 5.21 (m, 1H), 3.74 (s, methyl), 3.53 (m, 1H), alkane region 3.05 (m, 2H), 2.74 (m, 4H), 2.27 (m, 2H), 2.08 (m, 2H), 1.82 (m, 2H).
15. -1.
16. Minimization was achieved using Chem 3D Pro (illustrations shown) as well as Spartan 2002 software.