From BN-Naphthalenes to Benzoborole Dianions
From BN-Naphthalenes to Benzoborole Dianions
复制标题
从BN-萘到苯并硼杂二阴离子
DOI：
10.1002/chem.202101178
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Cui Chunming
中科院分区：
文献类型：
--
作者：
Zhu Dezhao;Guo Lulu;Li Jianfeng;Cui Chunming
研究了以碱金属还原BN -萘衍生物为原料，采用缩环策略合成苯并溴代阴离子的方法。在Et2O中还原1 -炔基2,1 -苄基aborine1导致炔基锂的消除，形成1 -氨基- 1 -苯并硼酸三锂盐t2 a，而还原1 -苯基2,1 -苯并硼酸四氢呋喃生成1 -苯基- 1 -苯并硼酸二锂盐t2 c，同时消除ArNHLi。三锂盐和二锂盐2和2已被充分表征。用Et3NHCl处理盐三锂，导致氨基锂选择性质子化，得到盐二锂，可以干净地氧化成1‐氨基‐1‐苯并硼酸，收率很高。1 -苯基- 1 -苯并硼酸二盐c与MeI反应生成硼酸锂c，该锂c在溶液和固体状态下都发光。
The synthesis of benzoborole dianions by alkali metal reduction of BN‐naphthalene derivatives via a ring‐contraction strategy has been developed. Reduction of 1‐alkynyl 2,1‐benzazaborine1 ain Et2O led to the elimination of alkynyllithium with the formation of 1‐amino‐1‐benzoborole trilithium salt2 a, whereas reduction of 1‐phenyl 2,1‐benzazaborine1 cin THF yielded 1‐phenyl‐1‐benzoborole dilithium salt2 cwith the elimination of ArNHLi. The trilithium and dilithium salts2 aand2 chave been fully characterized. Treatment of trilithium salt2 awith Et3NHCl led to the selective protonation of the amino lithium to afford the dilithium salt2 aH, which could be cleanly oxidized to 1‐amino‐1‐benzoborole3in an excellent yield. Reaction of 1‐phenyl‐1‐benzoborole dilithium salt2 cwith MeI yielded the lithium borate4 c, which is luminescent both in solution and in the solid state.