Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation

Gan, Yu1; Zhou, Jun-Feng1; Li, Xuejiao1; Liu, Ji-Ren2,3,4; Liu, Fang-Jie1; Hong, Xin2,5,6; Ye, Baihua1

2024-06-11

10.1021/jacs.4c04587

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

0002-7863

1520-5126

In the realm of organic synthesis, the catalytic and stereoselective formation of C-glycosidic bonds is a pivotal process, bridging carbohydrates with aglycones. However, the inherent chirality of the saccharide scaffold often has a substantial impact on the stereoinduction imposed by a chiral ligand. In this study, we have established an unprecedented zirconaaziridine-mediated asymmetric nickel catalysis, enabling the diastereoselective coupling of bench-stable glycosyl phosphates with a range of (hetero)aromatic and glycal iodides as feasible coupling electrophiles. Our developed method showcases a broad scope and a high tolerance for various functional groups. More importantly, precise stereocontrol toward both anomeric configurations of forming C(sp(2))-glycosides can be realized by simply utilizing the popular chiral bioxazoline (biOx) ligands in this reductive Ni catalysis. Regarding the operating mechanism, both experimental and computational studies support the occurrence of a redox transmetalation process, leading to the formation of a transient, bimetallic Ni-Zr species that acts as a potent and efficient single-electron reductant in the catalytic process.

SCI ; EI

英语

其他

ShanghaiTech University[2022YFA1504301] ; National Key R&D Program of China["22122109","22271253"] ; National Natural Science Foundation of China[LDQ23B020002] ; Zhejiang Provincial Natural Science Foundation of China[SN-ZJU-SIAS-006] ; Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study[BNLMS202102] ; Beijing National Laboratory for Molecular Sciences[JCTD-2021-11] ; CAS Youth Interdisciplinary Team["226-2022-00140","226-2022-00224","226-2023-00115"] ; Fundamental Research Funds for the Central Universities["ZJUCEU2020007","202210"] ; State Key Laboratory of Clean Energy Utilization[2022R01005]

Chemistry

Chemistry, Multidisciplinary

WOS:001245114700001

AMER CHEMICAL SOC

Web of Science

1.ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China
2.Zhejiang Univ, Ctr Chem Frontier Technol, Dept Chem, State Key Lab Clean Energy Utilizat, Hangzhou 310027, Peoples R China
3.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Shenzhen 518055, Peoples R China
4.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
5.Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
6.Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China

Gan, Yu,Zhou, Jun-Feng,Li, Xuejiao,et al. Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024,146(24).

Gan, Yu.,Zhou, Jun-Feng.,Li, Xuejiao.,Liu, Ji-Ren.,Liu, Fang-Jie.,...&Ye, Baihua.(2024).Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,146(24).

Gan, Yu,et al."Zirconaaziridine-Mediated Ni-Catalyzed Diastereoselective C(sp²)-Glycosylation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146.24(2024).