42270-91-7Relevant articles and documents
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Bayley,Knowles
, p. 2420,2421 (1978)
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Dimerization and trapping of diazirinyl radicals
Thompson, Robert A.,Francisco, Joseph S.,Grutzner, John B.
, p. 756 - 765 (2007/10/03)
Computational and experimental methods have been utilized to examine the facile dimerization of diazirinyl radicals. Two potential dimers were investigated using density functional theory. Both were shown to have low-barrier reaction coordinates leading t
Reactions and reactivity of acyloxycarbenes
Moss, Robert A.,Xue, Song,Liu, Weiguo,Krogh-Jespersen, Karsten
, p. 12588 - 12597 (2007/10/03)
Phenylacetoxycarbene, phenyl(pivaloyloxy)carbene, and phenyl(benzoyloxy)carbene, photolytically generated from diazirine precursors in pentane at 25°C, efficiently rearranged by 1,2-acyl migrations to give high yields of the appropriate 1,2-diketones. The kinetics of these rearrangements were determined by laser flash photolysis. Substituent effects on the acyl migrations and ab initio electronic structure calculations on ground state carbenes and transition states were employed to analyze the rearrangement mechanism. Additions of phenylacetoxycarbene to alkenes proceeded in good yields, in lieu of the 1,2-acyl shift; absolute rate constants were obtained for these reactions of the ambiphilic carbene. (Phenoxymethyl)acetoxycarbene gave only a 1,2-H shift; the potentially competitive 1,2-acetyl migration was suppressed.
