title: Unprecedented Oxycyanation of Methylenecyclopropanes for the Facile Synthesis of Benzoxazine Compounds Containing a Cyano Group.
abstract: A novel intramolecular oxycyanation of methylenecyclopropanes is reported that proceeds through oxidative cleavage of the N-CN bond and subsequent palladium transfer from N to O of the amide group. A range of substituted benzo[d][1,3]oxazines with a cyano group are readily furnished by this newly developed oxycyanation reaction. Tris(4-trifluoromethylphenyl)phosphine as a ligand has been found to be crucial to effectively promote the transformation with high chemo- and regioselectivity. Moreover, the reaction outcome can be significantly affected by the electronic effect of the acyl group attached to the nitrogen atom of methylenecyclopropanes. When R(3) is a chloromethyl group, the pyrrolo[2,3-b]quinoline derivative is obtained by thermal-induced [3+2] cycloaddition of methylenecyclopropane to the methanediimine intermediate.
authors: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Yu-Chao
authors: YC
authors: Yuan
authors: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
authors: Hai-Bin
authors: HB
authors: Yang
authors: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. siocxiangying@mail.sioc.ac.cn.
authors: Xiang-Ying
authors: XY
authors: Tang
authors: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. weiyin@mail.sioc.ac.cn.
authors: Yin
authors: Y
authors: Wei
authors: State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China. mshi@mail.sioc.ac.cn.
authors: Min
authors: M
authors: Shi
keywords: amides; benzoxazines; intramolecular oxycyanation; palladium; synthetic methods