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

Résultats de recherche: Contribution à un journal/une revue › Article › Revue par des pairs

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Résumé

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.

langue originale	Anglais
Pages (de - à)	609-616
Nombre de pages	8
journal	Comptes Rendus Chimie
Volume	20
Numéro de publication	6
Les DOIs	https://doi.org/10.1016/j.crci.2017.02.001
Etat de la publication	Publié - 1 juin 2017
Modification externe	Oui

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

1-s2.0-S1631074817300115-mainVersion finale publiée, 685 KBLicense: 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",

note = "Publisher Copyright: {\textcopyright} 2017 Acad{\'e}mie des sciences",

year = "2017",

month = jun,

day = "1",

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

language = "English",

volume = "20",

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journal = "Comptes Rendus Chimie",

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Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides andacetylenic aziridines. / Bochatay, Valentin; Debien, Laurent; Chemla, Fabrice et al.
Dans: Comptes Rendus Chimie, Vol 20, Numéro 6, 01.06.2017, p. 609-616.

Résultats de recherche: Contribution à un journal/une revue › Article › Revue par des pairs

TY - JOUR

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

UR - https://www.scopus.com/pages/publications/85016617227

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

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