CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2023 Jun 12;62(24):e202301422. doi: 10.1002/anie.202301422. Epub 2023 May 8.
Herein, a copper(I)-catalyzed asymmetric conjugate addition/protonation with selenols and α-substituted α,β-unsaturated thioamides is disclosed, which affords a series of chiral selenides in high to excellent enantioselectivity. As for both selenols and α-substituted α,β-unsaturated thioamides, the reaction enjoys broad substrate scopes. The present catalytic system is also successfully applied to asymmetric selenation of β-substituted α,β-unsaturated thioamides. A [Cu-(R,R )-TANIAPHOS]-SePh species is characterized by its Se NMR spectra, which gives a chemical shift at δ 462 ppm. Moreover, a {[Cu-(R)-TOL-BINAP]-SePh} species is characterized by X-ray analysis, which confirms the formation of Cu-Se bond in the reaction. Finally, the transformations of the thioamide group to amine and thioester are demonstrated to be straightforward.
本文报道了一种铜（I）催化的不对称共轭加成/质子化反应，涉及硒醇和α-取代的α,β-不饱和硫代酰胺，该反应以高至优秀的对映选择性得到了一系列手性硒化物。对于硒醇和α-取代的α,β-不饱和硫代酰胺，该反应具有广泛的底物范围。本催化体系还成功地应用于β-取代的α,β-不饱和硫代酰胺的不对称硒化反应。通过硒 NMR 光谱对[Cu-(R,R)-TANIAPHOS]-SePh 物种进行了表征，其化学位移在 δ 462 ppm 处。此外，通过 X 射线分析对{[Cu-(R)-TOL-BINAP]-SePh}物种进行了表征，证实了反应中形成了 Cu-Se 键。最后，还展示了将硫酰胺基转化为胺和硫酯的过程是直接的。
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