Issue 4, 2023

Pd(ii)-catalyzed β- and γ-C-(sp3)–H dienylation with allenyl acetates

Abstract

Recent years have seen the emergence of transition metal catalyzed C–H activation as a powerful synthetic tool in organic chemistry. Allenes have fascinated synthetic chemists due to their unique reactivity. While directing group assisted functionalization of C(sp2)–H bonds with allenes is well documented in the literature, their coupling with more challenging aliphatic C(sp3)–H bonds remains elusive. In this regard, we hereby report a Pd(II) catalyzed 8-aminoquinoline directed aliphatic C(sp3)–H dienylation protocol using allenyl acetates. A variety of carboxylic acids including fatty acids and amino acids were efficiently functionalized at β and γ-positions to afford diversely functionalized 1,3-dienes. Preliminary mechanistic studies revealed the crucial role of the base in the success of the transformation. The reaction proceeds via regioselective 2,3-migratory insertion of the allene with the alkylpalladium(II) species followed by β-acetoxy elimination.

Graphical abstract: Pd(ii)-catalyzed β- and γ-C-(sp3)–H dienylation with allenyl acetates

Supplementary files

Article information

Article type
Edge Article
Submitted
18 Sep 2022
Accepted
19 Dec 2022
First published
20 Dec 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 955-962

Pd(II)-catalyzed β- and γ-C-(sp3)–H dienylation with allenyl acetates

R. K. Shukla, A. M. Nair and C. M. R. Volla, Chem. Sci., 2023, 14, 955 DOI: 10.1039/D2SC05188E

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