From Isocyanides to Iminonitriles via Silver-mediated Sequential Insertion of C(sp3)–H Bond
Huiwen Chi,
Hao Li,
Bingxin Liu,
Rongxuan Ye,
Haoyang Wang,
Yin-Long Guo,
Qitao Tan,
Bin Xu
Affiliations
Huiwen Chi
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China
Hao Li
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China
Bingxin Liu
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China
Rongxuan Ye
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China; Qianweichang College, Shanghai University, Shanghai 200444, China
Haoyang Wang
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
Yin-Long Guo
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
Qitao Tan
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China; Corresponding author
Bin Xu
Department of Chemistry, Innovative Drug Research Center, Shanghai University, Shanghai 200444, China; State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China; Corresponding author
Summary: Heterocycles are prevalent constituents of many marketing drugs and biologically active molecules to meet modern medical challenges. Isocyanide insertion into C(sp3)–H bonds is challenging especially for the construction of quaternary carbon centers. Herein, we describe an efficient strategy for the synthesis of α-iminonitrile substituted isochromans and tetrahydroisoquinolines (THIQs) with quaternary carbon centers through silver-triflate-mediated sequential isocyanide insertion of C(sp3)–H bonds, where isocyanide acts as the crucial “CN” and “imine” sources. The produced α-iminonitriles have extensive applications as valuable synthetic building blocks for pharmacologically interesting heterocycles. This protocol could be further applied for the synthesis of iminonitrile-decorated phenanthridines and azapyrene. Interestingly, a remarkable aggregation-induced emission (AIE) effect was first observed for an iminonitrile-decorated pyrene derivative, which may open a particular area for iminonitrile applications in materials science. : Materials Chemistry; Optical Property; Organic Synthesis Subject Areas: Materials Chemistry, Optical Property, Organic Synthesis
