Synthesis of carbohydrate-derived (Z)-vinyl halides and silanes: Samarium-promoted stereoselective 1,2-elimination on sugar-derived α-halomethylcarbinol acetates

TETRAHEDRON

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Article

Soto, Martin¹  Soengas, Raquel G.^2,3,4  Silva, Artur M. S.^2,3  Gotor-Fernandez, Vicente¹  Rodriguez-Solla, Humberto¹ 

[1] Univ Oviedo, Dept Organ & Inorgan Chem, Julian Claveria 8, E-33006 Oviedo, Spain

[2] Univ Aveiro, Dept Chem, P-3810193 Aveiro, Portugal

[3] Univ Aveiro, QOPNA, P-3810193 Aveiro, Portugal

[4] Univ Almeria, Dept Chem & Phys, Almeria 04120, Spain

关键词: Carbohydrates;    Elimination;    Samarium;    Silanes;    Sonogashira reaction;    Stereoselectivity;    Vinyl halides;   

DOI  :  10.1016/j.tet.2018.05.002

来源: Elsevier

【 摘 要 】

A general and highly selective method for the synthesis of carbohydrate-derived (Z)-vinyl halides and silanes is described. This reaction takes place through a beta-elimination process of sugar-derived alpha-halomethylcarbinol acetates promoted by samarium diiodide. Starting materials have been easily prepared in two steps consisting in an initial addition of halomethyllithium compounds to the corresponding galactose-derived aldehyde, followed by acetylation. A mechanism that explains both the formation of (Z)-vinyl derivatives and its selectivity is proposed. Finally, the synthetic usefulness of these compounds has been applied in cross-coupling reactions with ethynyl benzene towards the formation of selected enyne derivatives. (C) 2018 Elsevier Ltd. All rights reserved.

【 授权许可】

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