Synthetic organic reactions mediated by sodium hydride

In synthetic organic chemistry, sodium hydride (NaH) has been utilized almost exclusively as a routine Brønsted base, while NaH has not been considered to work as a hydride donor. Recently, our group has serendipitously found that NaH can function as a unique hydride donor by its solvothermal treatment with sodium iodide (NaI) or lithium iodide (LiI) in tetrahydrofuran (THF) as a solvent. This discovery led to the development of unprecedented reductive molecular transformations such as hydrodecyanation of α-quaternary benzyl cyanides, controlled reduction of amides into aldehydes, dearylation of arylphopsphine oxides, and hydrodehalogenation of haloarenes. Moreover, this concise protocol allows for the use of NaH as enhanced Lewis acid and Brønsted base, enabling directed aromatic C-H sodiation, nucleophilic amination of methoxy arenes, and C2-amination of pyridines (the Chichibabin amination).Ministry of Education (MOE)Nanyang Technological UniversityThis work was supported by funding from Nanyang Technological University (NTU) Singapore and the Singapore Ministry of Education (Academic Research Fund Tier 1: 2015─T1─001─040). We thank Prof. Ryo Takita (University of Tokyo) and Prof. Hajime Hirao (City University of Hong Kong) for their computational studies on our reactions. Our co─workers whose names appear in the references are gratefully acknowledged for their intellectual and experimental contributions