Abstract

The Horner–Wadsworth–Emmons (HWE) reaction has become well established among existing methodologies for the highly stereoselective olefination of carbonyl compounds. The reliability of this reaction in terms of its robustness, high stereoselectivity, and broad substrate scope permit retrosynthetic disconnection of the olefin bond in α,β-unsaturated carbonyl intermediates in natural product synthesis. This review discusses recent applications of the HWE reaction in natural product synthesis, highlighting its use for carbon chain elongation, coupling reactions of synthetic segments, ring-closing reactions, tandem reactions including HWE olefination, and asymmetric reactions.

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