1. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs
- Author
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Florian Dulong, Alejandro Perez-Luna, Fabrice Chemla, Franck Ferreira, Institut Parisien de Chimie Moléculaire (IPCM), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Radical ,Dimethylzinc ,carbozincation ,chemistry.chemical_element ,Zinc ,010402 general chemistry ,Zinc atom ,01 natural sciences ,Full Research Paper ,lcsh:QD241-441 ,chemistry.chemical_compound ,Cascade reaction ,lcsh:Organic chemistry ,Polymer chemistry ,Organic chemistry ,tandem reaction ,lcsh:Science ,Carbenoid ,Alkyl ,chemistry.chemical_classification ,010405 organic chemistry ,carbometallation ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,Organic Chemistry ,radicals ,3. Good health ,0104 chemical sciences ,Chemistry ,chemistry ,13. Climate action ,Stereoselectivity ,lcsh:Q ,carbenoids - Abstract
The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxy)enoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.
- Published
- 2013