Noncovalent interaction-assisted ferrocenyl phosphine ligands in asymmetric catalysis

Zhao，Qingyang1; Chen，Caiyou3; Wen，Jialin2,5; Dong，Xiu Qin4; Zhang，Xumu2

2020-09-15

10.1021/acs.accounts.0c00347

ACCOUNTS OF CHEMICAL RESEARCH   影响因子和分区

0001-4842

1520-4898

ConspectusNoncovalent 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: CC bonds of substituted conjugate alkenes with neutral hydrogen bond acceptors, including nitro groups, carbonyl groups (ketones, esters, amides, maleinimides, and anhydrides), ethers, and sulfones; CN 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.

SCI

英语

通讯

National Natural Science Foundation of China[21602172] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Science, Technology and Innovation Commission of Shenzhen[JCYJ20190807155201669][KQTD20150717103157174] ; Fundamental Research Funds for the Central Universities[19ykpy140]

Chemistry

Chemistry, Multidisciplinary

WOS:000572833000019

AMER CHEMICAL SOC

CHEMISTRY

2-s2.0-85091125402

Scopus

1.School of Pharmaceutical Sciences (Shenzhen),Sun Yat-sen University,Shenzhen,518107,China
2.Shenzhen Grubbs Institute and Department of Chemistry,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518000,China
3.Division of Chemistry and Chemical Engineering,California Institute of Technology,Pasadena,91125,United States
4.College of Chemistry and Molecular Sciences,Wuhan University,Wuhan,430072,China
5.Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen,518000,China

Zhao，Qingyang,Chen，Caiyou,Wen，Jialin,et al. Noncovalent interaction-assisted ferrocenyl phosphine ligands in asymmetric catalysis[J]. ACCOUNTS OF CHEMICAL RESEARCH,2020,53(9):1905-1921.

Zhao，Qingyang,Chen，Caiyou,Wen，Jialin,Dong，Xiu Qin,&Zhang，Xumu.(2020).Noncovalent interaction-assisted ferrocenyl phosphine ligands in asymmetric catalysis.ACCOUNTS OF CHEMICAL RESEARCH,53(9),1905-1921.

Zhao，Qingyang,et al."Noncovalent interaction-assisted ferrocenyl phosphine ligands in asymmetric catalysis".ACCOUNTS OF CHEMICAL RESEARCH 53.9(2020):1905-1921.