铑催化的β-磺酰基-α,β-不饱和酮的高度化学选择性和对映选择性氢化反应：合成手性γ-酮砜
Highly Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of β-Sulfonyl-α,β-unsaturated Ketones: Access to Chiral γ-Ketosulfones.
作者信息
Liu Gang, Yin Congcong, Yang Xuanliang, Li Anqi, Wang Minyan, Zhang Xumu, Dong Xiu-Qin
机构信息
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.
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong 518055, P.R. China.
出版信息
Org Lett. 2021 Jan 1;23(1):19-24. doi: 10.1021/acs.orglett.0c03517. Epub 2020 Dec 22.
Rh-catalyzed highly chemo- and enantioselective hydrogenation of β-sulfonyl-α,β-unsaturated ketones was first successfully developed. Remarkably, a variety of enantioenriched γ-ketosulfones were generated in good to high yields with excellent chemo/enantioselectivities (82-99% yields, >99:1 chemoselectivity, 88 to >99% ee). Moreover, the gram-scale asymmetric hydrogenation was carried out smoothly in 97% yield and 97% ee. Preliminary DFT computations furnished a reasonable explanation for the high chemoselectivity and enantioselectivity.
首次成功开发了铑催化的β-磺酰基-α,β-不饱和酮的高度化学和对映选择性氢化反应。值得注意的是，生成了多种对映体富集的γ-酮砜，产率良好至高，具有优异的化学/对映选择性（产率82-99%，化学选择性>99:1，对映体过量88%至>99%）。此外，克级规模的不对称氢化反应顺利进行，产率为97%，对映体过量为97%。初步的密度泛函理论计算为高化学选择性和对映选择性提供了合理的解释。
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