Article

Multifunctional Ag(I)/CAAA-Amidphos Complex-Catalyzed Asymmetric [3 + 2] Cycloaddition of α-Substituted Acrylamides

Kaiqiang ZhangCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaQifu DengCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaJie LuoCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaChuliang GongCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaZhigang ChenCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaWei ZhongCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaShunqin HuCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. ChinaHaifei WangCollege of Life Science and Chemistry, Hunan University of Technology, Zhuzhou 412007, P. R. China

2021en

ABI

Abstract

Construction of two kinds of prevalent skeletons for chiral pyrrolidines bearing a quaternary stereocenter and bridged dinitrogen heterocycles is a long-standing challenge in synthetic organic chemistry. In this work, we introduce a multifunctional Ag(I)/CAAA-amidphos complex-catalyzed asymmetric [3 + 2] cycloaddition of α-substituted acrylamides with iminoesters as a powerful strategy for the construction of 4,4-disubstituted endoamidopyrrolidines (up to 98% yield, m/b > 99:1, 99% ee) and bridged 3,6-diazabicyclo[3.2.1]octanes (up to 97% yield, b/m > 99:1, >99% ee) in high yields with excellent enantioselectivities and ratios of mono- and bicyclic adducts. It was revealed by in situ 31P NMR and 1H NMR kinetic experiments analysis that the chiral Ag(I)/CAAA-amidphos complex, as a multifunctional catalytic system through synergistic activation and spatial orientation of the dipole and dipolarophile, first realized the asymmetric [3 + 2] cycloaddition of the poorly reactive α-substituted acrylamides.

Identifiers

DOI: 10.1021/acscatal.1c00913

Citations and references

Cited by 20 references

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