A Lewis acid-mediated synthesis of P-alkyl-substituted phosphaalkenes
A Lewis acid-mediated synthesis of P-alkyl-substituted phosphaalkenes
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DOI：
10.1039/c0nj00188k
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发表时间：
2010-01-01
影响因子：
3.3
通讯作者：
Gates, Derek P.
中科院分区：
文献类型：
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作者：
Bates, Joshua I.;Patrick, Brian O.;Gates, Derek P.
处理(RP)-P-1(SiMe3)(2)(R-1=Bu-t、Ad、Mes、Me3Si；Ad=1-金刚烷基，Mes=2,4,6-三甲基苯基)和(RC)-C-2(O)R-3(R-2:R-3=Bu-t:H、Ph:Ph、Bu-t:Bu-t、Bu-t:Ph的等摩尔混合物，通过 P-31 NMR 光谱监测，Bu-t:Me) 与 AlCl3 (1 当量) 得到相应的磷烯 (RP)-P-1=(CRR3)-R-2。该新方法应用于(RP)-P-1=(CRR3)-R-2的多重合成[1a: R-1 = Bu-t, R-2 = Bu-t, R-3 = H; 2a:R-1=Ad，R-2=Bu-t，R-3=H； 3a:R-1=Mes，R-2=Bu-t，R-3=H； 3b：R-1 = Mes，R-2 = R-3 = Ph]，分离收率良好（1a：80%；2a：57%；3a：63%；3b：76%）。以前未知的2a 已被完全表征。进行了 1a 和 2a 与第 13 族路易斯酸的反应性，以探究它们的反应性并提供一种在结构上表征这些 P-烷基磷烯的方法。 1a 中心点 AlCl3、1a 中心点 GaCl3 和 2a 中心点 GaCl3 的 X 射线晶体结构表明，Bu-t 取代基呈反式排列，P = C 键长符合预期（平均 1.64 埃）。
Treating an equimolar mixture of (RP)-P-1(SiMe3)(2) (R-1 = Bu-t, Ad, Mes, Me3Si; Ad = 1-adamantyl, Mes = 2,4,6-trimethylphenyl) and (RC)-C-2(O)R-3 (R-2:R-3 = Bu-t:H, Ph:Ph, Bu-t:Bu-t, Bu-t:Ph, Bu-t:Me) with AlCl3 (1 equiv.) affords the corresponding phosphaalkenes (RP)-P-1=(CRR3)-R-2 as monitored by P-31 NMR spectroscopy. This new method was applied to the multigram synthesis of (RP)-P-1=(CRR3)-R-2 [1a: R-1 = Bu-t, R-2 = Bu-t, R-3 = H; 2a: R-1 = Ad, R-2 = Bu-t, R-3 = H; 3a: R-1 = Mes, R-2 = Bu-t, R-3 = H; 3b: R-1 = Mes, R-2 = R-3 = Ph] in good isolated yields (1a: 80%; 2a: 57%; 3a: 63%; 3b: 76%). Previously unknown 2a has been fully characterized. The reactivity of 1a and 2a with group 13 Lewis acids was performed in an effort to probe their reactivity and provide a means to structurally characterize these P-alkyl phosphaalkenes. The X-ray crystal structures of 1a center dot AlCl3, 1a center dot GaCl3 and 2a center dot GaCl3 reveal that the Bu-t substituents are configured in a trans arrangement and the P = C bond lengths are as expected (avg. 1.64 angstrom).