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Collective asymmetric synthesis of the Strychnos alkaloids via thiophene S,S-dioxide cycloadditions

Abstract:

The Strychnos alkaloids have long been regarded as landmark targets for chemical synthesis due to their captivating architectures and notorious biological properties. However, the design of approaches that access multiple family members in an asymmetric, concise, and atom economical fashion remains a significant challenge. Here we show that thiophene S,S-dioxides (TDOs) offer a modular, rapid entry to the Strychnos natural products via inverse electron demand Diels-Alder cascades. Exceptional levels of stereocontrol are demonstrated in asymmetric TDO cycloadditions, which afforded tricyclic indolines of utility in medicinal chemistry research, and enabled stereoselective syntheses of eight Strychnos alkaloids by the shortest routes described to date, including the first synthesis of the iconic family member brucine. Using a machine-learning approach, computational studies provide insight into the source of stereoinduction, and reveal an intriguing and unexpected spontaneous cheletropic extrusion of SO2.

Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1038/s41557-025-02041-1

Authors

More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Chemistry
Sub department:
Chemistry Research Laboratory
Role:
Author


More from this funder
Funder identifier:
https://ror.org/0439y7842
Grant:
EP/X028674/1


Publisher:
Springer Nature
Journal:
Nature Chemistry More from this journal
Volume:
18
Issue:
4
Pages:
782-789
Publication date:
2026-01-23
Acceptance date:
2025-12-02
DOI:
EISSN:
1755-4349
ISSN:
1755-4330


Language:
English
Keywords:
Pubs id:
2345767
Local pid:
pubs:2345767
Deposit date:
2025-12-05
ARK identifier:

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