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(a) Higher temperatures led to a mixture of products consistent with a radical chain process where 4a was only a minor product. (b) Recently published computational results for enthalpies of the thermal cyclization depicted in Scheme 1b indicate a barrier of 55.8 kcal/mol and endothermicity of 19.3 kcal/mol: Kawatkar, S. P.; Schreiner, P. R. Org. Lett. 2002, 4, 3643-3646.
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0141439735
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note
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Photoirradiation of 2,5-diiodo-3,4-diphenylthiophene in hexanes in the absence of trapping agent exclusively yields 4a, indicating that formation of 5 or 7 from a thiophene monoradical is not facile.
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22
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0141662621
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note
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Vinyl diradical (8) is not trapped in the experiment, suggesting that either it does not form or that reactions competing with its trapping are more rapid than in the analogous hydrocarbon in ref 5c.
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Acetylenic ether photochemistry has also been proposed to involve cleavage of the weaker heteroatom-carbon bond; see: Smith, B. A.; Callinan, A. J.; Swenton, J. S. Tetrahedron Lett. 1994, 35, 2283-2286.
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Smith, B.A.1
Callinan, A.J.2
Swenton, J.S.3
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