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Photochemical Alkene Hydrophosphination with Bis(trichlorosilyl)phosphine
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2022-08-04 , DOI: 10.1021/jacs.2c05248 Michael B Geeson 1 , Keita Tanaka 1 , Rachid Taakili 2, 3 , Rachid Benhida 2, 3 , Christopher C Cummins 1
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2022-08-04 , DOI: 10.1021/jacs.2c05248 Michael B Geeson 1 , Keita Tanaka 1 , Rachid Taakili 2, 3 , Rachid Benhida 2, 3 , Christopher C Cummins 1
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Bis(trichlorosilyl)phosphine (HP(SiCl3)2, 1) was prepared from [TBA][P(SiCl3)2] ([TBA]2, TBA = tetra-n-butylammonium) and triflic acid in 36% yield. Phosphine 1 is an efficient reagent for hydrophosphination of unactivated terminal olefins under UV irradiation (15–60 min) and gives rise to bis(trichlorosilyl)alkylphosphines (RP(SiCl3)2, R = (CH2)5CH3, 88%; (CH2)7CH3, 98%; (CH2)2C(CH3)3, 76%; CH2Cy, 93%; (CH2)2Cy, 95%; CH2CH(CH3)(CH2)2CH3, 82%; (CH2)3O(CH2)3CH3, 95%; (CH2)3Cl, 83%; (CH2)2SiMe3, 92%; (CH2)5C(H)CH2, 44%) in excellent yields. The products require no further purification beyond filtration and removal of volatile material under reduced pressure. The P–Si bonds of prototypical products RP(SiCl3)2 (R = −(CH2)5CH3, −(CH2)7CH3) are readily functionalized to give further phosphorus-containing products: H3C(CH2)7PCl2 (56%), [H3C(CH2)5P(CH2Ph)3]Br (84%), H3C(CH2)7PH2 (61%), H3C(CH2)5P(O)(H)(OH) (81%), and H3C(CH2)5P(O)(OH)2 (55%). Experimental mechanistic investigations, accompanied by quantum chemical calculations, point toward a radical-chain mechanism. Phosphine 1 enables the fast, high-yielding, and atom-efficient preparation of compounds that contain phosphorus–carbon bonds in procedures that bypass white phosphorus (P4), a toxic and high-energy intermediate of the phosphorus industry.
中文翻译：
双（三氯甲硅烷基）膦的光化学烯烃氢膦化反应
双(三氯甲硅烷基)膦 (HP(SiCl 3 ) 2 , 1 ) 由 [TBA][P(SiCl 3 ) 2 ] ([TBA] 2 , TBA = 四正丁基铵) 和三氟甲磺酸制备，产率为 36% . 膦1是一种有效的试剂，可在紫外线照射下（15-60 分钟）对未活化的末端烯烃进行氢膦化反应，生成双（三氯甲硅烷基）烷基膦（RP(SiCl 3 ) 2 , R = (CH 2 ) 5 CH 3 , 88% ; (CH 2 ) 7 CH 3 , 98%; (CH 2 ) 2C(CH 3 ) 3 , 76%; CH 2 Cy, 93%; (CH 2 ) 2 Cy, 95%; CH 2 CH(CH 3 )(CH 2 ) 2 CH 3 , 82%; (CH 2 ) 3 O(CH 2 ) 3 CH 3 , 95%; (CH 2 ) 3 Cl, 83%; (CH 2 ) 2 SiMe 3 , 92%; (CH 2 ) 5 C(H)CH 2, 44%) 以优异的产量。除了过滤和减压除去挥发性物质外，产物不需要进一步纯化。原型产物 RP(SiCl 3 ) 2 (R = -(CH 2 ) 5 CH 3 , -(CH 2 ) 7 CH 3 ) 的 P-Si 键很容易被官能化以得到进一步的含磷产物： H 3 C( CH 2 ) 7 PCl 2 (56%), [H 3 C(CH 2 ) 5 P(CH 2 Ph) 3 ]Br (84%), H 3 C(CH 2) 7 PH 2 (61%)、H 3 C(CH 2 ) 5 P(O)(H)(OH) (81%) 和 H 3 C(CH 2 ) 5 P(O)(OH) 2 ( 55%）。伴随着量子化学计算的实验机械研究指向自由基链机制。磷化氢1能够在绕过磷工业的有毒和高能中间体白磷 (P 4 )的过程中快速、高产和原子效率地制备含有磷-碳键的化合物。
更新日期：2022-08-04
中文翻译：
双（三氯甲硅烷基）膦的光化学烯烃氢膦化反应
双(三氯甲硅烷基)膦 (HP(SiCl 3 ) 2 , 1 ) 由 [TBA][P(SiCl 3 ) 2 ] ([TBA] 2 , TBA = 四正丁基铵) 和三氟甲磺酸制备，产率为 36% . 膦1是一种有效的试剂，可在紫外线照射下（15-60 分钟）对未活化的末端烯烃进行氢膦化反应，生成双（三氯甲硅烷基）烷基膦（RP(SiCl 3 ) 2 , R = (CH 2 ) 5 CH 3 , 88% ; (CH 2 ) 7 CH 3 , 98%; (CH 2 ) 2C(CH 3 ) 3 , 76%; CH 2 Cy, 93%; (CH 2 ) 2 Cy, 95%; CH 2 CH(CH 3 )(CH 2 ) 2 CH 3 , 82%; (CH 2 ) 3 O(CH 2 ) 3 CH 3 , 95%; (CH 2 ) 3 Cl, 83%; (CH 2 ) 2 SiMe 3 , 92%; (CH 2 ) 5 C(H)CH 2, 44%) 以优异的产量。除了过滤和减压除去挥发性物质外，产物不需要进一步纯化。原型产物 RP(SiCl 3 ) 2 (R = -(CH 2 ) 5 CH 3 , -(CH 2 ) 7 CH 3 ) 的 P-Si 键很容易被官能化以得到进一步的含磷产物： H 3 C( CH 2 ) 7 PCl 2 (56%), [H 3 C(CH 2 ) 5 P(CH 2 Ph) 3 ]Br (84%), H 3 C(CH 2) 7 PH 2 (61%)、H 3 C(CH 2 ) 5 P(O)(H)(OH) (81%) 和 H 3 C(CH 2 ) 5 P(O)(OH) 2 ( 55%）。伴随着量子化学计算的实验机械研究指向自由基链机制。磷化氢1能够在绕过磷工业的有毒和高能中间体白磷 (P 4 )的过程中快速、高产和原子效率地制备含有磷-碳键的化合物。
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