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. 2023 May 11;13(20):13511-13515.
doi: 10.1039/d3ra02430j. eCollection 2023 May 2.

Stereoselective synthesis of (E)-α,β-unsaturated esters: triethylamine-catalyzed allylic rearrangement of enol phosphates

Yulong Zhang  1 , Huichuang Guo  1 , Qian Wu  1 , Xiaojing Bi  1 , Enxue Shi  1 , Junhua Xiao  1
Affiliations

Stereoselective synthesis of (E)-α,β-unsaturated esters: triethylamine-catalyzed allylic rearrangement of enol phosphates

Yulong Zhang et al. RSC Adv. .

Abstract

α,β-Unsaturated esters are key structural motifs widely distributed in various biologically active molecules, and their Z/E-stereoselective synthesis has always been considered highly attractive in organic synthesis. Herein, we present a >99% (E)-stereoselective one-pot synthetic approach towards β-phosphoroxylated α,β-unsaturated esters via a mild trimethylamine-catalyzed 1,3-hydrogen migration of the corresponding unconjugated intermediates derived from the solvent-free Perkow reaction between low-cost 4-chloroacetoacetates and phosphites. Versatile β,β-disubstituted (E)-α,β-unsaturated esters were thus afforded with full (E)-stereoretentivity by cleavage of the phosphoenol linkage via Negishi cross-coupling. Moreover, a stereoretentive (E)-rich mixture of a α,β-unsaturated ester derived from 2-chloroacetoacetate was obtained and both isomers were easily afforded in one operation.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Selected bioactive α,β-unsaturated carbonyl motifs.
Scheme 1
Scheme 1. E-Stereoselective synthesis of α,β-unsaturated esters from enol phosphates.
Scheme 2
Scheme 2. Perkow reaction of phosphite with chloroacetoacetate.
Scheme 3
Scheme 3. Preparation of (Z) and (E) isomers of 6a in one operation.
Scheme 4
Scheme 4. Proposed (E)-stereospecific allylic rearrangement mechanism.
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