Direct allylic C–H alkylation of enol silyl ethers enabled by photoredox–Brønsted base hybrid catalysis

Kohsuke Ohmatsu, Tsubasa Nakashima, Makoto Sato and Takashi Ooi ()
Additional contact information
Kohsuke Ohmatsu: Nagoya University
Tsubasa Nakashima: Nagoya University
Makoto Sato: Nagoya University
Takashi Ooi: Nagoya University

Nature Communications, 2019, vol. 10, issue 1, 1-7

Abstract: Abstract Strategies for altering the reaction pathway of reactive intermediates are of significant importance in diversifying organic synthesis. Enol silyl ethers, versatile enolate equivalents, are known to undergo one-electron oxidation to generate the radical cations that spontaneously form electrophilic α-carbonyl radicals via elimination of the silyl groups. Here, we demonstrate that close scrutiny of the property of the radical cations as strong C–H acids enables the identification of a catalyst system consisting of an iridium-based photosensitizer and 2,4,6-collidine for the generation of nucleophilic allylic radicals from enol silyl ethers through one-electron oxidation-deprotonation sequence under light irradiation without the desilylation of the radical cation intermediates. The resultant allylic radicals engage in the addition to electron-deficient olefins, establishing the selective allylic C-H alkylation of enol silyl ethers. This strategy is broadly applicable, and the alkylated enol silyl ethers can be transformed into highly functionalized carbonyl compounds by exploiting their common polar reactivity.

Date: 2019
References: Add references at CitEc
Citations: View citations in EconPapers (1)

Downloads: (external link)
https://www.nature.com/articles/s41467-019-10641-y 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:10:y:2019:i:1:d:10.1038_s41467-019-10641-y

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

DOI: 10.1038/s41467-019-10641-y

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 () and Springer Nature Abstracting and Indexing ().