Tris(bicyclo[1.1.1]pentyl)phosphine: An Exceptionally Small Tri- tert -alkylphosphine and Its Bis-Ligated Pd(0) Complex
Tris(bicyclo[1.1.1]pentyl)phosphine: An Exceptionally Small Tri- tert -alkylphosphine and Its Bis-Ligated Pd(0) Complex
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三(双环[1.1.1]戊基)膦：一种极小的三叔烷基膦及其双配位Pd(0)络合物
DOI：
10.1021/jacs.3c00885
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发表时间：
2023
影响因子：
15
通讯作者：
Schley, Nathan D.
中科院分区：
文献类型：
--
作者：
Perry, Griffin L.;Schley, Nathan D.
三(双环[1.1.1]戊基)膦可以通过PH3与[1.1.1]正丙烷自由基加成得到已知最小的三叔烷基膦。PBcp3比PCy3小得多，在给电子能力方面与PEt3相当。它给出了一个双连接的Pd(0)络合物Pd(PBcp3)2，它对卤代烷的氧化加成反应非常活跃，并作为一种通用配体用于钯催化的SP3亲电体的交叉偶联。将[1.1.1]正丙烷与苯基膦自由基加成得到双(双环[1.1.1]戊基)膦衍生物PBcp2Ph，说明了该方法对合成双环戊基膦的通用性。
Tris(bicyclo[1.1.1]pentyl)phosphine can be prepared by radical addition of PH3to [1.1.1]propellane, giving the smallest tri-tert-alkylphosphine known. PBcp3is substantially smaller than PCy3and is comparable in electron-donating power to PEt3. It gives a bis-ligated Pd(0) complex Pd(PBcp3)2that is exceptionally reactive toward alkyl halide oxidative addition and functions as a general ligand for palladium-catalyzed cross-coupling of sp3electrophiles. Radical addition of [1.1.1]propellane to phenylphosphine gives the bis(bicyclo[1.1.1]pentyl)phosphine derivative PBcp2Ph, illustrating the generality of this approach to bicyclopentylphosphine synthesis.