Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization

Chen，Yang Bo1; Liu，Li Gao1; Chen，Can Ming1; Liu，Yi Xi1; Zhou，Bo1; Lu，Xin1; Xu，Zhou2; Ye，Long Wu1,3,4

2023-06-05

10.1002/anie.202303670

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

Axially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well-established axially chiral 6-membered biaryl skeletons, examples of 5-membered biaryls have been quite scarce, and mono-substituted 3-arylpyrrole atropisomers have not been reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X−H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono-substituted 3-arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation-involved cyclization and elucidate the origin of enantioselectivity.

Alkynes Asymmetric Catalysis Axial Chirality Cyclizations Heterocycles

SCI ; EI ; IC ; CCR

英语

NI论文

其他

National Natural Science Foundation of China[22121001];National Natural Science Foundation of China[22125108];National Natural Science Foundation of China[92056104];

Chemistry

Chemistry, Multidisciplinary

WOS:000977791900001

WILEY-V C H VERLAG GMBH

20231814035057

Catalysis ; Chelation ; Enantioselectivity ; Ligands ; Positive ions

Physical Chemistry:801.4 ; Chemical Reactions:802.2

CHEMISTRY

2-s2.0-85153891685

Scopus

1.State Key Laboratory of Physical Chemistry of Solid Surfaces,Key Laboratory of Chemical Biology of Fujian Province,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China
2.Jiangsu Key Laboratory of New Drug Research and Clinical Pharmacy,School of Pharmacy,Xuzhou Medical University,Xuzhou,221004,China
3.State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai,200032,China
4.Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518055,China

Chen，Yang Bo,Liu，Li Gao,Chen，Can Ming,et al. Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization[J]. Angewandte Chemie - International Edition,2023,62(23).

Chen，Yang Bo.,Liu，Li Gao.,Chen，Can Ming.,Liu，Yi Xi.,Zhou，Bo.,...&Ye，Long Wu.(2023).Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization.Angewandte Chemie - International Edition,62(23).

Chen，Yang Bo,et al."Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization".Angewandte Chemie - International Edition 62.23(2023).