摘要
A new synthetic route to functionalized neutral and anionic azadiphospholes from easily accessible starting materials is described. Equimolar reaction of Na(OCP) and N-(2,6-dimethylphenyl) pivalimidoyl chloride 2a cleanly affords the imidoxy-functionalized 1,2,4-azadiphosphole 3a. Using Na(OCP) and imidoyl chloride in a 2: 1 ratio leads to an anionic four-membered ring Na[4a], which has been structurally characterized. During 16h at room temperature, Na[4a] rearranges to the anionic 1,3,4-azadiphospholide Na[5a] with release of carbon monoxide. Applying the more sterically demanding N-(2,6-diisopropylphenyl) pivalimidoyl chloride allows isolation of the 1,3,4-azadiphospholide Na[5b] in good yield (> 70 %). Possible mechanisms leading to the new isomeric azadiphospholides have been investigated with the aid of high-level composite calculations.
- 出版日期2016-10
- 单位中山大学