Vinyl Grignard-Mediated Stereoselective Carbocyclization of Lactone Acetals

Christinne Hedberg; Morten Estrup; Espen Z. Eikeland; Henrik H. Jensen

doi:10.1021/acs.joc.7b03079

Vinyl Grignard-Mediated Stereoselective Carbocyclization of Lactone Acetals

Christinne Hedberg, Morten Estrup, Espen Z. Eikeland, Henrik H. Jensen^*

^*Corresponding author af dette arbejde

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

9 Citationer (Scopus)

Abstract

A novel Ferrier-type carbocyclization is reported. It involves a carbohydrate-derived lactone acetal synthesized from methyl α-d-glucopyranoside, which upon treatment with excess vinylmagnesium bromide provides a highly substituted carbocyclic product as a single stereoisomer. The yield is greatly increased when N,N,N′,N′-tetramethylethylenediamine is added to the reaction mixture. Optimized reaction conditions have been applied to lactone acetals derived from other carbohydrates. Based on the obtained results, a possible reaction mechanism has been proposed. Furthermore, scalability of the reaction up to 15 g scale and derivatization of the carbocyclic product has been demonstrated, including the formation of a rare trans-bicyclo[4.3.0]nonene scaffold via a ring-closing metathesis. The structure of this and all carbocyclic products were confirmed by X-ray crystallographic analysis.

Originalsprog	Engelsk
Tidsskrift	Journal of Organic Chemistry
Vol/bind	83
Nummer	4
Sider (fra-til)	2154-2165
Antal sider	12
ISSN	0022-3263
DOI	https://doi.org/10.1021/acs.joc.7b03079
Status	Udgivet - 16 feb. 2018

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Citationsformater

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abstract = "A novel Ferrier-type carbocyclization is reported. It involves a carbohydrate-derived lactone acetal synthesized from methyl α-d-glucopyranoside, which upon treatment with excess vinylmagnesium bromide provides a highly substituted carbocyclic product as a single stereoisomer. The yield is greatly increased when N,N,N′,N′-tetramethylethylenediamine is added to the reaction mixture. Optimized reaction conditions have been applied to lactone acetals derived from other carbohydrates. Based on the obtained results, a possible reaction mechanism has been proposed. Furthermore, scalability of the reaction up to 15 g scale and derivatization of the carbocyclic product has been demonstrated, including the formation of a rare trans-bicyclo[4.3.0]nonene scaffold via a ring-closing metathesis. The structure of this and all carbocyclic products were confirmed by X-ray crystallographic analysis.",

author = "Christinne Hedberg and Morten Estrup and Eikeland, {Espen Z.} and Jensen, {Henrik H.}",

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T1 - Vinyl Grignard-Mediated Stereoselective Carbocyclization of Lactone Acetals

AU - Hedberg, Christinne

AU - Estrup, Morten

AU - Eikeland, Espen Z.

AU - Jensen, Henrik H.

PY - 2018/2/16

Y1 - 2018/2/16

N2 - A novel Ferrier-type carbocyclization is reported. It involves a carbohydrate-derived lactone acetal synthesized from methyl α-d-glucopyranoside, which upon treatment with excess vinylmagnesium bromide provides a highly substituted carbocyclic product as a single stereoisomer. The yield is greatly increased when N,N,N′,N′-tetramethylethylenediamine is added to the reaction mixture. Optimized reaction conditions have been applied to lactone acetals derived from other carbohydrates. Based on the obtained results, a possible reaction mechanism has been proposed. Furthermore, scalability of the reaction up to 15 g scale and derivatization of the carbocyclic product has been demonstrated, including the formation of a rare trans-bicyclo[4.3.0]nonene scaffold via a ring-closing metathesis. The structure of this and all carbocyclic products were confirmed by X-ray crystallographic analysis.

AB - A novel Ferrier-type carbocyclization is reported. It involves a carbohydrate-derived lactone acetal synthesized from methyl α-d-glucopyranoside, which upon treatment with excess vinylmagnesium bromide provides a highly substituted carbocyclic product as a single stereoisomer. The yield is greatly increased when N,N,N′,N′-tetramethylethylenediamine is added to the reaction mixture. Optimized reaction conditions have been applied to lactone acetals derived from other carbohydrates. Based on the obtained results, a possible reaction mechanism has been proposed. Furthermore, scalability of the reaction up to 15 g scale and derivatization of the carbocyclic product has been demonstrated, including the formation of a rare trans-bicyclo[4.3.0]nonene scaffold via a ring-closing metathesis. The structure of this and all carbocyclic products were confirmed by X-ray crystallographic analysis.

UR - http://www.scopus.com/inward/record.url?scp=85042183334&partnerID=8YFLogxK

U2 - 10.1021/acs.joc.7b03079

DO - 10.1021/acs.joc.7b03079

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SN - 0022-3263

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SP - 2154

EP - 2165

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 4

ER -

Vinyl Grignard-Mediated Stereoselective Carbocyclization of Lactone Acetals

Abstract

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