An Iron-Catalyzed Route to Dewar 1,3,5-Triphosphabenzene and Subsequent Reactivity
An Iron-Catalyzed Route to Dewar 1,3,5-Triphosphabenzene and Subsequent Reactivity
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铁催化杜瓦瓶 1,3,5-三磷苯的路线及后续反应
DOI：
10.1002/ange.202208663
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发表时间：
2022
影响因子：
--
通讯作者：
Barrett A
中科院分区：
文献类型：
--
作者：
Barrett A
将[Fe(Salen)]2-2，4，6‐tris(triphenylmethyl)‐Dewar‐1，3，5‐triphosphabenzene-oxo(1)催化剂上的炔环三聚反应应用于三苯基甲基磷杂炔(2)，可得到克数量级的μ(3)。体积大的锂盐LiHMDS有助于3重排为1，3，5-三磷苯价异构体(3‘)，随后经历有趣的磷迁移反应，形成环收缩物种(3’)。密度泛函理论计算为这种重排提供了一种合理的机制。考虑到3的稳定性，我们研究了一系列前所未有的变化。我们报道了成功的亲核/亲电加成和质子化/氧化反应的新的结晶学表征产物。
The application of an alkyne cyclotrimerization regime with an [Fe(salen)]2‐μ‐oxo (1) catalyst to triphenylmethylphosphaalkyne (2) yields gram‐scale quantities of 2,4,6‐tris(triphenylmethyl)‐Dewar‐1,3,5‐triphosphabenzene (3). Bulky lithium salt LiHMDS facilitates a rearrangement of3to the 1,3,5‐triphosphabenzene valence isomer (3′), which subsequently undergoes an intriguing phosphorus migration reaction to form the ring‐contracted species (3′′). Density functional theory calculations provide a plausible mechanism for this rearrangement. Given the stability of3, a diverse array of unprecedented transformations was investigated. We report novel crystallographically characterized products of successful nucleophilic/electrophilic addition and protonation/oxidation reactions.