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Noncovalent Interaction-Assisted Ferrocenyl Phosphine Ligands in Asymmetric Catalysis

Zhao, Qingyang and Chen, Caiyou and Wen, Jialin and Dong, Xiu-Qin and Zhang, Xumu (2020) Noncovalent Interaction-Assisted Ferrocenyl Phosphine Ligands in Asymmetric Catalysis. Accounts of Chemical Research, 53 (9). pp. 1905-1921. ISSN 0001-4842. https://resolver.caltech.edu/CaltechAUTHORS:20200827-145552489

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Abstract

Noncovalent interactions are ubiquitous in nature and are responsible for the precision control in enzyme catalysis via the cooperation of multiple active sites. Inspired by this principle, noncovalent interaction-assisted transition metal catalysis has emerged recently as a powerful tool and has attracted intense interest. However, it is still highly desirable to develop efficient and operationally convenient ligands along this line with new structural motifs. Based on the specific nature of hydrogen bonding and ion pairing interactions, we developed a series of noncovalent interaction-assisted chiral ferrocenyl phosphine ligands, including Zhaophos, Wudaphos, and miscellaneous SPO-Wudaphos. Due to the assistance of noncovalent interactions, this catalytic mode is capable of achieving transition metal catalyzed asymmetric hydrogenation and other transformations with remarkable improvement of reactivity and selectivity. In some specific challenging cases, this probably represents one of the most productive methods. Moreover, these ligands are easily prepared, air stable, and highly tunable, meeting the requirements of industrial application. In this Account, we give a concise review of recent advances in asymmetric catalysis. By means of hydrogen bonding interactions, Rh- and Ir-Zhaophos complexes exhibited excellent activities and enantioselectivities in asymmetric hydrogenation of a wide range of substrates: C═C bonds of substituted conjugate alkenes with neutral hydrogen bond acceptors, including nitro groups, carbonyl groups (ketones, esters, amides, maleinimides, and anhydrides), ethers, and sulfones; C═N bonds of substituted iminium salts with chloride as an anionic hydrogen bond acceptor, including N–H imines and cyclic imines; N-heteroaromatic compounds with HCl as an additive, including unprotected quinolines, isoquinolines, and indoles; carbocation of substituted oxocarbenium ions. By means of ion pairing interactions, Rh-Wudaphos complexes enabled the catalytic asymmetric hydrogenation of α-substituted unsaturated carboxylic acids, carboxy-directed α,α-disubstituted terminal olefins, and sodium α-arylethenylsulfonates. Rh-SPO-Wudaphos utilized both hydrogen bonding and ion pairing interactions in asymmetric hydrogenation of α-substituted unsaturated carboxylic acids and phosphonic acids. In addition, Zhaophos has achieved highly selective intramolecular reductive amination and inter- and intramolecular asymmetric decarboxylative allylation. Investigations into mechanism implied that noncovalent interactions were involved in the catalytic cycle and played a critical role for both high reactivity and selectivity. Notably, a rare ionic hydrogenation pathway has been proposed in some cases. Furthermore, these catalytic systems have been used in the gram-scale synthesis of natural products and pharmaceuticals.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.accounts.0c00347DOIArticle
ORCID:
AuthorORCID
Zhao, Qingyang0000-0001-8259-4321
Chen, Caiyou0000-0001-7536-7139
Wen, Jialin0000-0003-3328-3265
Dong, Xiu-Qin0000-0002-5045-1198
Zhang, Xumu0000-0001-5700-0608
Additional Information:© 2020 American Chemical Society. Received: June 6, 2020; Published: August 27, 2020. We are grateful for our co-workers’ contributions and financial support from the National Natural Science Foundation of China (No. 21602172), the Guangdong Provincial Key Laboratory of Catalysis (No. 2020B121201002), the Science, Technology and Innovation Commission of Shenzhen (JCYJ20190807155201669, KQTD20150717103157174), and the Fundamental Research Funds for the Central Universities (No. 19ykpy140). Author Contributions: Q.Z. and C.C. contributed equally. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Natural Science Foundation of China21602172
Guangdong Provincial Key Laboratory of Catalysis2020B121201002
Science, Technology and Innovation Commission of ShenzhenJCYJ20190807155201669
Science, Technology and Innovation Commission of ShenzhenKQTD20150717103157174
Fundamental Research Funds for the Central Universities19ykpy140
Subject Keywords:Stereoselectivity, Ions, Organic compounds, Noncovalent interactions, Hydrogenation
Issue or Number:9
Record Number:CaltechAUTHORS:20200827-145552489
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200827-145552489
Official Citation:Noncovalent Interaction-Assisted Ferrocenyl Phosphine Ligands in Asymmetric Catalysis. Qingyang Zhao, Caiyou Chen, Jialin Wen, Xiu-Qin Dong, and Xumu Zhang. Accounts of Chemical Research 2020 53 (9), 1905-1921; DOI: 10.1021/acs.accounts.0c00347
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105135
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Aug 2020 22:10
Last Modified:16 Sep 2020 23:13

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