Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines

Valentin Bochatay; Laurent Debien; Fabrice Chemla; Franck Ferreira; Olivier Jackowski; Alejandro Perez-Luna

doi:10.1016/j.crci.2017.02.001

Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines

Valentin Bochatay, Laurent Debien, Fabrice Chemla, Franck Ferreira, Olivier Jackowski, Alejandro Perez-Luna

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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.

Original language	English
Pages (from-to)	609-616
Number of pages	8
Journal	Comptes Rendus Chimie
Volume	20
Issue number	6
DOIs	https://doi.org/10.1016/j.crci.2017.02.001
Publication status	Published - 1 Jun 2017
Externally published	Yes

Keywords

Alkynes
Carbenoids
Rearrangement
Silicon
Zinc

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10.1016/j.crci.2017.02.001Licence: CC BY-NC-ND

1-s2.0-S1631074817300115-mainFinal published version, 685 KBLicence: CC BY-NC-ND

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title = "Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines",

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. ",

keywords = "Alkynes, Carbenoids, Rearrangement, Silicon, Zinc",

author = "Valentin Bochatay and Laurent Debien and Fabrice Chemla and Franck Ferreira and Olivier Jackowski and Alejandro Perez-Luna",

year = "2017",

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doi = "10.1016/j.crci.2017.02.001",

language = "English",

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journal = "Comptes Rendus Chimie",

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T1 - Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines

AU - Bochatay, Valentin

AU - Debien, Laurent

AU - Chemla, Fabrice

AU - Ferreira, Franck

AU - Jackowski, Olivier

AU - Perez-Luna, Alejandro

PY - 2017/6/1

Y1 - 2017/6/1

N2 - 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.

AB - 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.

KW - Alkynes

KW - Carbenoids

KW - Rearrangement

KW - Silicon

KW - Zinc

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U2 - 10.1016/j.crci.2017.02.001

DO - 10.1016/j.crci.2017.02.001

M3 - Article

SN - 1631-0748

VL - 20

SP - 609

EP - 616

JO - Comptes Rendus Chimie

JF - Comptes Rendus Chimie

IS - 6

ER -

Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines

Abstract

Keywords

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