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Mechanistic implications of stereospecific 1,5-hydrogen-atom transfer in the formation of an unusual allene/enoate photoproduct

✍ Scribed by Curtis A. Hastings; Josef D. Ringgenberg; Erick M. Carreira


Publisher
Elsevier Science
Year
1997
Tongue
French
Weight
219 KB
Volume
38
Category
Article
ISSN
0040-4039

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✦ Synopsis


Irradiation of allene-enoate 1 affords alkyne 3 as the major photoproduct.

Selectively deuterated analog d-I affords a single diastereomer on inadiation. This result .~bim~/ical a sl~pwise mechanism for enantioselective [2+2]-photocycloadditioas involving a 1,4intermediate 2 which collapses to products more rapidly than it unde~oes reversion to stinting material, resulting in the observed high levels of asymmetric induction.