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Ji et al. Chem Synth 2022;2:17 Chemical Synthesis
DOI: 10.20517/cs.2022.27

Research Article Open Access

Enantioselective 1,1-diarylation of terminal alkenes

catalyzed by palladium with a chiral phosphoric acid

1,#
1,#
1
Kai Ji , Jie Huang , Xin-Yu Zhang , Zhi-Min Chen 1,2,*
1
School of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai
Jiao Tong University, Shanghai 200240, China.
2
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, Gansu, China.
#
Authors contributed equally to this work.
Correspondence to: Prof. Zhi-Min Chen, School of Chemistry and Chemical Engineering, Shanghai Key Laboratory for Molecular
Engineering of Chiral Drugs, Shanghai Jiao Tong University, No. 800, Dongchuan Road, Minhang District, Shanghai 200240,
China. E-mail: chenzhimin221@sjtu.edu.cn
How to cite this article: Ji K, Huang J, Zhang XY, Chen ZM. Enantioselective 1,1-diarylation of terminal alkenes catalyzed by
palladium with a chiral phosphoric acid. Chem Synth 2022;2:17. https://dx.doi.org/10.20517/cs.2022.27

Received: 13 Sep 2022 First Decision: 21 Sep 2022 Revised: 28 Sep 2022 Accepted: 9 Oct 2022 Published: 13 Oct 2022

Academic Editor: Feng Shi Copy Editor: Peng-Juan Wen Production Editor: Peng-Juan Wen

Abstract
The enantioselective 1,1-diarylation of allyl sulfones and vinyl sulfones is reported for the first time, enabled by a
combination of Pd dba and a chiral SPINOL-derived phosphoric acid. Various chiral sulfones containing 1,1-
3
2
diarylalkane motifs were obtained in moderate to good yields with moderate to high enantioselectivities. Control
experiments suggested that the sulfone group plays a key role in providing enantioselectivity and reactivity control
and might serve as a directing group.
Keywords: Cooperative catalysis, 1, 1-diarylation, allyl sulfone, chiral sulfone, chiral anion phase-transfer catalysis

INTRODUCTION
The chiral 1,1-diarylalkane motif is found in many bioactive natural products and pharmaceuticals
[1,2]
[Scheme 1A] . Accordingly, much effort has been devoted to developing methods for the enantioselective
[3-7]
synthesis of such structures . Among the methodologies that have been devised, the transition-metal
catalyzed asymmetric 1,1-diarylation of commercially available alkenes is one of the most straightforward
and adjustable strategies for the synthesis of chiral compounds containing a 1,1-diarylalkane motif and has
therefore attracted increasing attention . The Sigman group first reported the enantioselective 1,1-
[8,9]

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