A comparative study of the decomposition of o-alkynyl-substituted aryl diazo ketones. Synthesis of polysubstituted .beta.-naphthols via arylketene intermediates

Abstract

The photochemical, thermal, and rhodium-catalyzed decomposition reactions of several closely related o-alkynyl or o-alkenyl α-diazoaceto- and propiophenone derivatives have been studied. The reaction outcome is markedly dependent upon the reaction conditions employed for nitrogen extrusion. Thermolysis or photolysis of o-alkynyl α-diazopropiophenone derivatives yields polysubstituted β-naphthols. These products are derived from Wolff rearrangement of the initially formed carbene to give an aryl ketene which undergoes intramolecular cyclization onto the o-alkynyl substituent. In direct contrast to the thermal and photochemical results, Rh(II)-catalyzed decomposition yields products derived from direct attack of a rhodium carbenoid onto the tethered π-system producing a vinyl carbenoid intermediate