Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines - 31/03/17

Doi : 10.1016/j.crci.2017.02.001

Valentin N. Bochatay, Laurent Debien, Fabrice Chemla ^⁎ , Franck Ferreira ^⁎ , Olivier Jackowski, Alejandro Perez-Luna ^⁎
Sorbonne Universités, UPMC Université Paris-6, CNRS UMR 8232, Institut parisien de chimie moléculaire, 75005, Paris, France

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Abstract

Lithium alkynyl(disilyl)zincates obtained from metalated ethynyloxiranes, as well as from N-tert-butanesulfinyl(ethynyl)aziridines or N-tert-butanesulfonyl(ethynyl)aziridines, undergo 1,2-migration of the organosilyl group with ring opening of the oxirane or aziridine ring by S_Ni displacement. A developed protocol that involves nBuLi for the metalation step offers a straightforward approach to the corresponding δ-oxy- and δ-amino α-silyl allenylzinc intermediates. The reagents derived from the epoxides are amenable to subsequent in situ condensation with aldehydes or ketones to provide 1,3-diols but not those derived from aziridines that only react sluggishly in similar condensations.

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Keywords : Alkynes, Carbenoids, Rearrangement, Silicon, Zinc