Aliphatic diazo compounds. IX. The base-induced dimerization of α-diazo ketones
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چکیده
منابع مشابه
Lewis base mediated halogenation/semipinacol rearrangement of diazo compounds: new access to α-halo-quaternary ketones.
A novel halogenation/semipinacol rearrangement of α-diazo alcohol catalyzed by Lewis base has been developed through a carbene-free mechanism. This semipinacol transposition, initiated by an electrophilic halogenation (X = Cl(+), Br(+), and I(+)) of diazo carbon event, furnished a convenient synthetic route for the efficient synthesis of α-halo-quaternary ketones under mild conditions.
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Metal-diazo radicals of α-carbonyl diazomethanes are new members of the radical family and are precursors to metal-carbene radicals. Herein, using electron paramagnetic resonance spectroscopy with spin-trapping, we detect diazo radicals of α-carbonyl diazomethanes, induced by [Rh(I)Cl(cod)]2, [Co(II)(por)] and PdCl2, at room temperature. The unique quintet signal of the Rh-diazo radical was obs...
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[reaction: see text] A large and normal nitrogen-15 kinetic isotope effect of 1.035 +/- 0.003 provides direct support for the proposed mechanism for the rhodium-catalyzed carbene formation from diazo compounds, which involves the fast formation of a metal-diazo complex followed by rate-limiting extrusion of N2. The large magnitude of the KIE indicates extensive C-N bond fission in the transitio...
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ژورنال
عنوان ژورنال: Canadian Journal of Chemistry
سال: 1969
ISSN: 0008-4042,1480-3291
DOI: 10.1139/v69-665