Wolff rearrangement of β??alkynyl?螃窿?diazo?螃漫?ketoesters: light??induced acetylene–allene isomerization and its use for activation of enediynes

NG Zhegalova, VV Popik

Index: Zhegalova, Natalia G.; Popik, Vladimir V. Journal of Physical Organic Chemistry, 2011 , vol. 24, # 10 p. 969 - 975

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Citation Number: 9

Abstract

Abstract Irradiation of β-phenylethynyl-α-diazo-β-ketoester with 300 or 350 nm light results in efficient and regioselective Wolff rearrangement producing only the product of alkynyl group migration. Addition of alcohols to the resulting α-oxoketene yields α-phenylethynyl-β-diester, which undergoes rapid (τ< 1 min) tautomerization to 1, 1-dicarbalkoxyallene. The latter then adds second molecule of alcohol in Michael fashion to form the final product, 2-(1-alkoxy- ...