title: Silicon-based bulky group-induced remote control and conformational preference in the synthesis and application of isolable atropisomeric amides with secondary alcohol or amine moieties.
abstract: Remote stereocontrol through conformational transmission along a carbon chain is highly important in synthetic systems and molecular architectures. In this work, the interactional reactivity between a remote silicon-based bulky group and an O-/N-containing functional group has been revealed and determined by lateral lithiation-substitution, desilylation, as well as desilylation-olefination with benzaldehyde. The results suggest considerable information transmission and steric hindrance that can be exploited for the controllable synthesis of atropisomeric molecules. Based on the remote steric effect of a functional group across the aromatic ring of an amide, the construction of isolable atropisomeric amides with functional groups, such as alcohol, amine, and olefin was successfully achieved. All these new atropisomers were obtained in reasonable yield in pure diastereomeric form, and the specific configuration of representative products was confirmed by X-ray crystallography.
authors: State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, and University of the Chinese Academy of Sciences, Beijing (P. R. China), Fax: (+86) 931-4968129; Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310012 (P. R. China).
authors: Xing-Feng
authors: XF
authors: Bai
authors: Wen-Hui
authors: WH
authors: Deng
authors: Zheng
authors: Z
authors: Xu
authors: Fu-Wei
authors: FW
authors: Li
authors: Yuan
authors: Y
authors: Deng
authors: Chun-Gu
authors: CG
authors: Xia
authors: Li-Wen
authors: LW
authors: Xu
keywords: lithiation; olefination; organosilicon; remote control; stereoselective chemistry