An Azophosphine Synthetic Equivalent of Mesitylphosphaazide and Its 1,3-Dipolar Cycloaddition Reactions
An Azophosphine Synthetic Equivalent of Mesitylphosphaazide and Its 1,3-Dipolar Cycloaddition Reactions
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异亚苯基磷酰肼的偶氮膦合成等价物及其1,3-偶极环加成反应
DOI：
10.1021/jacs.1c03333
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发表时间：
2021
影响因子：
15
通讯作者：
Cummins, Christopher C.
中科院分区：
文献类型：
--
作者：
Riu, Martin-Louis Y.;Transue, Wesley J.;Rall, Jan M.;Cummins, Christopher C.
二苯并-7-磷杂降冰片二烯取代的二氮烯MesN 2 PA（1，其中Mes =均三甲苯基，A=蒽或C14 H10）是均三甲苯基叠氮磷（MesN 2 P）和蒽的合成等价物，通过在四氢呋喃中用[MesN 2]OTf（OTf = CF 3SO 3-）处理[Ph 3BPA][Na（OEt 2）2]（14%分离产率）合成。用不饱和分子环辛炔、[Na（二氧六环）2.5][OCP]（磷炔酸盐）和Ad-C-N-（2-氨基苯基）磷炔酸酯环加合物（[3][Na（12-冠-4）2]）的结构数据在单晶X射线衍射研究中获得。P2 A2是一种热活化的蒽基分子前体，可与1反应生成二氮杂三磷杂环戊二烯（diazatriphosphole）。苯-d 6中的1在33-65 °C下导致蒽挤出。该过程具有单分子动力学特征，其活化参数为ΔH ε = 21.6 ± 0.3 kcal/mol和ΔS ε = −4.9 ± 0.8 cal/（mol K）。
Dibenzo-7-phosphanorbornadiene-substituted diazene MesN2PA(1, where Mes = mesityl,A= anthracene, or C14H10), a synthetic equivalent of mesitylphosphaazide (MesN2P) and anthracene, was synthesized by treatment of [Ph3BPA][Na(OEt2)2] with [MesN2]OTf (OTf = CF3SO3–) in thawing tetrahydrofuran (14% isolated yield). Treatment of1with unsaturated molecules cyclooctyne, [Na(dioxane)2.5][OCP] (phosphaethynolate), and Ad–C≡P (Ad = adamantyl) results in the corresponding [3 + 2] phosphaazide-(phospha)alkyne cycloadducts, with concomitant loss of anthracene in 65%, 49%, and 38% isolated yield, respectively. Structural data for the phosphaethynolate cycloadduct ([3][Na(12-crown-4)2]) were obtained in a single-crystal X-ray diffraction study. A diazatriphosphole was generated by combining1with P2A2, a thermally activated anthracene-based molecular precursor to diphosphorus (P2). Thermolysis (33–65 °C) of1in benzene-d6leads to anthracene extrusion. This process has a unimolecular kinetic profile and proceeds with activation parameters of ΔH⧧= 21.6 ± 0.3 kcal/mol and ΔS⧧= −4.9 ± 0.8 cal/(mol K).