The catalytic enantioselective [1,2]-Wittig rearrangement cascade of allylic ethers

Kang, Tengfei; O’Yang, Justin; Kasten, Kevin; Allsop, Samuel; Lewis-Atwell, Toby; Farrar, Elliot H. E.; Juhl, Martin; Cordes, David; McKay, Aidan P.; Grayson, Matthew N.; Smith, Andrew D.

doi:10.1038/s41557-025-02022-4

articleNature ChemistryJan 6, 2026HYBRID OA

The catalytic enantioselective [1,2]-Wittig rearrangement cascade of allylic ethers

TKTengfei Kang JOJustin O’Yang KKKevin Kasten SASamuel Allsop TLToby Lewis-Atwell

University of St Andrews · Shaanxi Normal University · +1 more institution

PubMed

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Abstract

The catalytic enantioselective [1,2]-Wittig rearrangement of allylic ethers constitutes a recognized synthetic challenge as it is traditionally considered to arise from a non-concerted reaction pathway via formation and recombination of radical pairs. Here we show a catalytic enantioselective solution to this challenge, demonstrating that [1,2]-Wittig products are generated via an alternative reaction cascade to traditional dogma. The developed process employs a chiral bifunctional iminophosphorane catalyst to promote an initial enantioselective [2,3]-sigmatropic rearrangement. A subsequent base-promoted, stereoconvergent, fragmentation-recombination process that proceeds with high enantiospecificity and…

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Topics

Keywords

Enantioselective synthesis
Allylic rearrangement
Catalysis
Bifunctional
Cascade
Chirality (physics)

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