Atroposelective Synthesis of Axially Chiral N‐Arylpyrroles by Chiral‐at‐Rhodium Catalysis. Issue 32 (3rd June 2020)

• Record Type: Journal Article
• Authors: Ye, Chen‐Xi; Chen, Shuming; Han, Feng; Xie, Xiulan; Ivlev, Sergei; Houk, K. N.; Meggers, Eric
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 32(2020)
• Page Start: 13552
• Page End: 13556
• Publication Date: 2020-06-03
• Subjects: atroposelective reactions -- chiral biaryls -- chiral-at-metal complexes -- homogeneous catalysis -- N-arylpyrroles; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202004799
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved with a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid. Specifically, N‐arylpyrroles were alkylated with N‐acryloyl‐1 H ‐pyrazole electrophiles in up to 93 % yield and with up to >99.5 % ee, and follow‐up conversions reveal the synthetic utility of this new method. DFT calculations elucidate the origins of the observed excellent atroposelectivity. Abstract : Freeze, don't move : A transformation of fluxional into configurationally stable axially chiral N‐arylpyrroles was achieved through a highly atroposelective electrophilic aromatic substitution catalyzed by a chiral‐at‐metal rhodium Lewis acid, with follow‐up transformations leading to structurally diverse axially chiral N‐arylpyrroles.