Chiral sulfide and achiral sulfonic acid cocatalyzed enantioselective electrophilic tandem selenylation semipinacol rearrangement of allenols

Ren-Fei Cao, Ruirui Su, Zheng-Wei Wei, Ze-Long Li, Deng Zhu, Yu-Xuan Huo, Xiao-Song Xue (xuexs@sioc.ac.cn) and Zhi-Min Chen (chenzhimin221@sjtu.edu.cn)
Additional contact information
Ren-Fei Cao: Shanghai Jiao Tong University
Ruirui Su: 1 Sub-lane Xiangshan
Zheng-Wei Wei: Shanghai Jiao Tong University
Ze-Long Li: Shanghai Jiao Tong University
Deng Zhu: Shanghai Jiao Tong University
Yu-Xuan Huo: Shanghai Jiao Tong University
Xiao-Song Xue: 1 Sub-lane Xiangshan
Zhi-Min Chen: Shanghai Jiao Tong University

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: Abstract A highly enantioselective electrophilic selenylation/semipinacol rearrangement of allenols has been developed, which is enabled by the cooperative catalysis of a chiral sulfide and an achiral sulfonic acid. The designed and synthesized chiral sulfide catalyst and selenylating reagent play a crucial role in enhancing both enantioselectivity and reactivity. This approach exhibits excellent regio-, chemo-, and enantioselectivity, providing access to diverse enantioenriched cyclopentanones featuring an arylselenovinyl-substituted quaternary carbon stereocenter. Furthermore, these products can be transformed into synthetically valuable alkyne, vinyl bromide, and aniline derivatives. Mechanistic studies reveal that the combination of a chiral sulfide and an achiral sulfonic acid not only facilitates the formation of catalytically active species, but also governs the enantioselectivity of the reaction. Meanwhile, density functional theory calculations disclose that four hydrogen bond interactions and a π‧‧‧π interaction are responsible for the observed enantioselectivity.

Date: 2025
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-025-57381-w Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57381-w

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-025-57381-w

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla (sonal.shukla@springer.com) and Springer Nature Abstracting and Indexing (indexing@springernature.com).