Studies toward norzoanthamine: Ireland-Claisen rearrangements of α,β-unsaturated esters in a stereocontrolled synthesis of trans-fused 2-cyclohexen-1-ones

TETRAHEDRON

卷:95

Article

Williams, David R.¹  Gladen, Paul T.¹  Patnaik, Samarjit¹ 

[1] Indiana Univ, Dept Chem, 800 E Kirkwood Ave, Bloomington, IN 47405 USA

关键词: IrelandeClaisen rearrangements;    Stereoselectivity;    Modified Henry reaction;    Nitroalkenes;    4 pi+2 pi cycloaddition reactions;    Olefin metathesis;   

DOI  :  10.1016/j.tet.2021.132354

来源: Elsevier

【 摘 要 】

The enantiocontrolled preparation of the trans-fused ABC ring system of norzoanthamine is described. The synthesis strategy has incorporated studies of Ireland-Claisen rearrangements of esters derived from 3,3-dimethylacrylic acid. Stereocontrol results from competing chair-and boat-like transition states. Introduction of a nitroalkene by application of a modified Henry reaction facilitates an intramolecular Diels-Alder cycloaddition for an effective and simple transformation to the desired conjugated decalone. A fully functionalized AB ring system leads to the cyclization of the trans-fused cyclohexenone to complete the ABC system via ring-closing metathesis. (C) 2021 Elsevier Ltd. All rights reserved.

【 授权许可】

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