Rhodium-Catalyzed Atroposelective C–H Arylation: Efficient Synthesis of Axially Chiral Heterobiaryls

• Published in: Journal of the American Chemical Society Vol. 141; no. 24; pp. 9504 - 9510
• Main Authors: Wang, Qiang, Cai, Zhong-Jian, Liu, Chen-Xu, Gu, Qing, You, Shu-Li
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.06.2019; Amer Chemical Soc
• Subjects: alcohols; allylation; arylation; benzaldehyde; carbon-hydrogen bond activation; catalysts; catalytic activity; Chemistry; Chemistry, Multidisciplinary; enantioselectivity; ethylene; ligands; nitrogen oxides; Physical Sciences; rhodium; Science & Technology; BRONSTED ACID; FUNCTIONALIZATION; ACTIVATION; BIARYL ATROPISOMERS; OLEFINATION; ENANTIOSELECTIVE SYNTHESIS; LIGANDS; NATURAL-PRODUCTS; PROGRESS; ALDEHYDES
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.9b03862

Rhodium­(I)-catalyzed atroposelective C–H arylation of heterobiaryls was presented. In the presence of a Rh catalyst derived from [Rh­(C2H4)2Cl]2 and a TADDOL-derived monodentate phosphonite, with 2-pyridine, 2-isoquinoline and their analogs as directing groups, a series of axially chiral heterobiaryls were obtained in excellent yields and enantioselectivities (up to 99% yield, 97% ee) via C–H direct functionalization reaction. The products obtained from this method provide a platform for the synthesis of axially chiral biaryl ligands and catalysts. As a demonstration, a chiral N-oxide synthesized from the product in one step could act as an efficient catalyst for asymmetric allylation of benzaldehyde with allyltrichlorosilane, leading to homoallyl alcohol with excellent enantiocontrol.