Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction

He, Shi-Jiang1,2; Shen, Boming1,2; Zuo, Lian-Zheng1,2; Xiang, Shao-Hua1,2,3; Liu, Huan-Huan1,2; Yu, Peiyuan1,2; Tan, Bin1,2

2024-07-01

10.1021/jacs.4c04024

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   影响因子和分区

0002-7863

1520-5126

Anthracenylidene is an intriguing structural unit with potential in various fields. The study presents a novel approach to introducing axial chirality into this all-carbon core skeleton through a remotely controlled desymmetrization strategy. A palladium-catalyzed enantioselective Heck arylation of exocyclic double bond of anthracene with two distinct substituents at the C10 position is harnessed to realize such a transformation. The judicious identification of the P-centrally chiral ligand is pivotal to ensure the competitive competence in reactivity and stereocontrol when the heteroatom handle is absent from the anthracenylidene skeleton. Both C10 mono- and disubstituted substrates were compatible for the established catalytic system, and structurally diverse anthracenylidene-based frameworks were forged with good-to-high enantiocontrol. The subsequent derivatization of the obtained products yielded a valuable array of centrally and axially chiral molecules, thus emphasizing the practicality of this chemistry. DFT calculations shed light on the catalytic mechanism and provided insights into the origin of the experimentally observed enantioselectivity for this reaction.

SCI

英语

第一 ; 通讯

National Natural Science Foundation of China["22425011","22301124","22231004","22271135"] ; National Key R&D Program of China["2022YFA1503703","2021YFF0701604"] ; Guangdong Innovative Program[2019BT02Y335] ; Guangdong Basic and Applied Basic Research Foundation[2024B1515020055] ; Shenzhen Science and Technology Program["KQTD20210811090112004","JCYJ20210324120205016","JCYJ20210324105005015"]

Chemistry

Chemistry, Multidisciplinary

WOS:001261332200001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
3.Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies, Shenzhen 518055, Peoples R China

He, Shi-Jiang,Shen, Boming,Zuo, Lian-Zheng,et al. Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024.

He, Shi-Jiang.,Shen, Boming.,Zuo, Lian-Zheng.,Xiang, Shao-Hua.,Liu, Huan-Huan.,...&Tan, Bin.(2024).Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.

He, Shi-Jiang,et al."Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2024).