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Sayed et al. Chem Synth 2023;3:20 Chemical Synthesis
DOI: 10.20517/cs.2023.05

Research Highlight Open Access

Pd-H/Lewis base cooperative catalysis confers

asymmetric allylic alkylation of esters atom-
economy and stereodivergence

Mostafa Sayed, Zhi-Yong Han, Liu-Zhu Gong *

Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China.
Correspondence to: Prof. Liu-Zhu Gong, Department of Chemistry, University of Science and Technology of China, No.96,
JinZhai Road Baohe District, Hefei 230026, Anhui, China. E-mail: gonglz@ustc.edu.cn
How to cite this article: Sayed M, Han ZY, Gong LZ. Pd-H/Lewis base cooperative catalysis confers asymmetric allylic alkylation
of esters atom-economy and stereodivergence. Chem Synth 2023;3:20. https://dx.doi.org/10.20517/cs.2023.05
Received: 1 Feb 2023 First Decision: 27 Feb 2023 Revised: 21 Mar 2023 Accepted: 3 Apr 2023 Published: 20 Apr 2023

Academic Editors: Bao-Lian Su, Da-Gang Yu Copy Editor: Ying Han Production Editor: Ying Han

Abstract
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The construction of Csp -Csp with high stereoselectivity, even in a stereodivergent way, has been a long-standing
theme in organic synthesis. As an atom- and step-economic transformation, transition metal hydride-mediated
allylic alkylation of enolizable carbonyl compounds with readily available allenes, alkynes or 1,3-dienes as the
unconventional allylating reagents has recently emerged as a promising protocol for the stereoselective
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construction of Csp -Csp bonds with high efficiency. Due to their less enolizability and weak nucleophilicity, simple
esters remain challenging substrates for these coupling reactions. On the other hand, the strategy of metal/organo
combined catalysis has recently emerged as one of the wide-ranging disciplines and powerful tools in asymmetric
synthesis. Considering the recent achievements of chiral Lewis base catalysis in catalytic asymmetric α-
functionalization of esters through a “rebound” mechanism, the cooperative combination of chiral Lewis bases and
metal hydride catalysis may offer great opportunities to the aforementioned chemistry. Recently, the groups of
Snaddon and Zi have made remarkable progresses in this area through palladium and chiral Lewis base cooperative
catalysis.

Keywords: Combined catalysis, chiral Lewis base, asymmetric catalysis, allenes, dienes

The construction of Csp -Csp with high stereoselectivity, even in a stereodivergent way, has been a long-
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standing theme in organic synthesis. As an atom- and step-economic transformation, transition metal

© The Author(s) 2023. Open Access This article is licensed under a Creative Commons Attribution 4.0
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