Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates.
iScience. 2019 Sep 27; 19:63-73.I

Abstract

Chiral cyclic sulfamidates are useful building blocks to construct compounds, such as chiral amines, with important applications. Often these compounds can only be generated through expensive precious metal catalysts. Here, Ni(OAc)2/(S, S)-Ph-BPE-catalyzed highly efficient asymmetric hydrogenation of cyclic sulfamidate imines was successfully developed, affording various chiral cyclic sulfamidates with high yields and excellent enantioselectivities (up to 99% yield, >99% enantiomeric excess [ee]). This Ni-catalyzed asymmetric hydrogenation on a gram scale has been achieved with only 0.1 mol% catalyst loading in 99% yield with 93% ee. Other types of N-sulfonyl ketimines were also hydrogenated well to obtain the corresponding products with >99% conversion, 96%-97% yields, and 97%->99% ee. In addition, this asymmetric methodology could produce other enantioenriched organic molecules, such as chiral β-fluoroamine, amino ether, and phenylglycinol. Moreover, a reasonable catalytic cycle was provided according to the deuterium-labeling studies, which could reveal a possible mechanism for this Ni-catalyzed asymmetric hydrogenation.

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Authors+Show Affiliations

Liu Y

Yi Z

Tan X

Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen, Guangdong 518055, P. R. China.

Dong XQ

Zhang X

Key Laboratory of Biomedical Polymers, Engineering Research Center of Organosilicon Compounds & Materials, Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, Hubei 430072, P. R. China; Department of Chemistry, Shenzhen Grubbs Institute, Southern University of Science and Technology, Shenzhen, Guangdong 518055, P. R. China. Electronic address: zhangxm@sustc.edu.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31352194

Citation

Liu, Yuanhua, et al. "Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates." IScience, vol. 19, 2019, pp. 63-73.

Liu Y, Yi Z, Tan X, et al. Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates. iScience. 2019;19:63-73.

Liu, Y., Yi, Z., Tan, X., Dong, X. Q., & Zhang, X. (2019). Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates. IScience, 19, 63-73. https://doi.org/10.1016/j.isci.2019.07.004

Liu Y, et al. Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates. iScience. 2019 Sep 27;19:63-73. PubMed PMID: 31352194.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates. AU - Liu,Yuanhua, AU - Yi,Zhiyuan, AU - Tan,Xuefeng, AU - Dong,Xiu-Qin, AU - Zhang,Xumu, Y1 - 2019/07/04/ PY - 2019/03/28/received PY - 2019/06/11/revised PY - 2019/06/28/accepted PY - 2019/7/29/pubmed PY - 2019/7/29/medline PY - 2019/7/29/entrez KW - Catalysis KW - Chemistry KW - Organic Chemistry KW - Stereochemistry SP - 63 EP - 73 JF - iScience JO - iScience VL - 19 N2 - Chiral cyclic sulfamidates are useful building blocks to construct compounds, such as chiral amines, with important applications. Often these compounds can only be generated through expensive precious metal catalysts. Here, Ni(OAc)2/(S, S)-Ph-BPE-catalyzed highly efficient asymmetric hydrogenation of cyclic sulfamidate imines was successfully developed, affording various chiral cyclic sulfamidates with high yields and excellent enantioselectivities (up to 99% yield, >99% enantiomeric excess [ee]). This Ni-catalyzed asymmetric hydrogenation on a gram scale has been achieved with only 0.1 mol% catalyst loading in 99% yield with 93% ee. Other types of N-sulfonyl ketimines were also hydrogenated well to obtain the corresponding products with >99% conversion, 96%-97% yields, and 97%->99% ee. In addition, this asymmetric methodology could produce other enantioenriched organic molecules, such as chiral β-fluoroamine, amino ether, and phenylglycinol. Moreover, a reasonable catalytic cycle was provided according to the deuterium-labeling studies, which could reveal a possible mechanism for this Ni-catalyzed asymmetric hydrogenation. SN - 2589-0042 UR - https://www.unboundmedicine.com/medline/citation/31352194/Nickel_Catalyzed_Asymmetric_Hydrogenation_of_Cyclic_Sulfamidate_Imines:_Efficient_Synthesis_of_Chiral_Cyclic_Sulfamidates_ DB - PRIME DP - Unbound Medicine ER -

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Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates.iScience. 2019 Sep 27; 19:63-73.I