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C 1-Symmetric Ligand-Enabled Stereoselective Formal [5+4] Cycloadditions of Palladium-Containing 1,5-Carbodipoles

211 Pages Posted: 8 May 2020 Publication Status: Review Complete

See all articles by Xing-Xing Yang

Xing-Xing Yang

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education

Guang-Yao Ran

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education

Chen Chen

Third Military Medical University

Jing-Fei Yue

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education

Wei Du

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education

Ying-Chun Chen

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education

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Abstract

The zwitterions bearing a π-allylmetal moiety, as highly reactive dipoles, have been employed for various asymmetric cycloadditions for the synthesis of diverse chiral carbo- and heterocycles. However, the reported all-carbon-based dipoles are generally limited to 1,3- or 1,4-type ones. Here, we disclose a new type of cyclic 1,5-carbodipoles, generated from the carbonates of 4-hydroxy-2-cyclopentenones under palladium catalysis via a deprotonation strategy, which can undergo highly asymmetric formal [5+4] cycloadditions with diverse 1-aza/oxadienes. New C1-symmetric bisphosphines containing two electronically and sterically different binding units or even hybrid phosphine/sulfonamide ligands from simple chiral sources are developed, which prove to be much superior to classical C2-symmetric ligands regarding the catalytic activity and stereoselectivity. Moreover, diastereodivergent catalysis could be realized for some substrate assemblies via ligand-control. Both 1,5-carbodipole species and chiral C1-symmetric ligands would find more application in asymmetric synthesis.

Keywords: carbodipole, palladium, C1-symmetric, ligand design, [5+4] cycloaddition

Suggested Citation

Yang, Xing-Xing and Ran, Guang-Yao and Chen, Chen and Yue, Jing-Fei and Du, Wei and Chen, Ying-Chun, C 1-Symmetric Ligand-Enabled Stereoselective Formal [5+4] Cycloadditions of Palladium-Containing 1,5-Carbodipoles. Available at SSRN: https://ssrn.com/abstract=3582692 or http://dx.doi.org/10.2139/ssrn.3582692
This is a paper under consideration at Cell Press and has not been peer-reviewed.

Xing-Xing Yang

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education ( email )

China

Guang-Yao Ran

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education ( email )

China

Chen Chen

Third Military Medical University

Chongqing
China

Jing-Fei Yue

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education ( email )

China

Wei Du

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education ( email )

China

Ying-Chun Chen (Contact Author)

Sichuan University - Key Laboratory of Drug-Targeting and Drug Delivery System of the Ministry of Education ( email )

China

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