Visible light-induced 1,2-alkoxy shift of α-diazoacetates for Wolff rearrangements – access to oxyketenes

DOI zum Zitieren der Version auf EPub Bayreuth: https://doi.org/10.15495/EPub_UBT_00009364
URN to cite this document: urn:nbn:de:bvb:703-epub-9364-6

Title data

Liu, Yang ; Xie, Zi-Yi ; Kloene, Lennard ; Xu, Cong-Lun ; Tai, Jian-Peng ; Zhu, Yu ; Cai, Bao-Gui ; Pan, Chongqing ; Koenigs, Rene M. ; Xuan, Jun:
Visible light-induced 1,2-alkoxy shift of α-diazoacetates for Wolff rearrangements – access to oxyketenes.
In: Chemical Science. Vol. 17 (2026) Issue 7 . - pp. 3587-3592.
ISSN 2041-6539
DOI der Verlagsversion: https://doi.org/10.1039/D5SC08263C

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Project information

Project title:	Project's official title Project's id Linux-Cluster zum wissenschaftlichen Hochleistungsrechnen 422127126
Project financing:	Deutsche Forschungsgemeinschaft

Abstract

The Wolff rearrangement is an important transformation to access ketenes via 1,2-alkyl or aryl migrations of α-diazoketones. In contrast, alkoxy group migration from free singlet carbenes has remained elusive owing to the intrinsically low migratory aptitude of alkoxy groups. Here we report a visible-light-induced 1,2-alkoxy/aryloxy shift of α-diazoacetates that generates oxy-substituted ketenes. These intermediates undergo efficient [2 + 2] cycloadditions with imines and nucleophilic addition reactions with amines. The method tolerates a wide substrate range, operates on gram scale, and is supported by mechanistic and computational studies. This work expands the scope of Wolff rearrangements and opens new chemical space for oxyketene reactivity.

Further data

Item Type:	Article in a journal
DDC Subjects:	500 Science > 540 Chemistry
Institutions of the University:	Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry - Univ.-Prof. Dr. René M. Koenigs Faculties Faculties > Faculty of Biology, Chemistry and Earth Sciences Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Organic Chemistry II - Bioorganic Chemistry
Language:	English
Originates at UBT:	Yes
URN:	urn:nbn:de:bvb:703-epub-9364-6
Date Deposited:	29 May 2026 07:43
Last Modified:	29 May 2026 07:44
URI:	https://epub.uni-bayreuth.de/id/eprint/9364

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