A Study on P-C Bond Activation Reaction Catalyzed by a Transition-Metal Complex

过渡金属配合物催化P-C键活化反应的研究

• 批准号: 02640479
• 负责人: NAKAZAWA Hiroshi
• 金额: $ 1.34万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640479/
• 关键词: P-C bond activation; Catalysis; alpha-Ketophosphonate; Decarbonylation; Metathesis; 脱カルボニル化反応; 触媒反応; Pd錯体; Ni錯体

Various alpha-ketophosphonates, RC(O)P(O)(OR')_2, are catalytically decarbonylated to give phosphonates, RP(O)(OR')_2, on treatment with PdR_2L_2(R = Me, Et ; L = tertiary phosphine), Pd(PPh_3)_4, or Pd(PCy_3)_2. Crossover experiments of two kinds of alpha-ketophosphonates revealed that a metathesis reaction at a P-C bond of an alpha-ketophosphonate takes place prior to the decarbonylation in the presence of a catalytic amount of palladium complex(R^1C(O)P(O)(OR^2)_2 + R^3C(O)p(O)(OR^4)_2 <double arrow> R^1C(O)P(O)(OR^4)_2 + R^3C(O)P(O)(OR^2)_2. The reaction of trans-PdEt_2(PMe_3)_2 with RC(O)P(O)(OR')_2 for a several minutes in a toluene reflux condition affords transPd(PMe_3)_2(C(O)R)(P(O)(OR')_2) as yellow crystals. The isolated palladium complexes yield the corresponding phosphonate in toluene at the reflux temperature and also serve as a catalyst of the decarbonylation and metathesis reactions of alpha-ketophosphonates. The overall catalytic decarbonylation reaction is proposed to consist of oxidative addition of RC(O)P(O)(OR')_2 at a P-C bond to a "PdL_2" species generated from PdR_2L_2 or PdL_4 to give trans-PdL_2(C(O)R)(P(O)(OR')_2), followed by decarbonylation of the C(O)R ligand to give PdL_2R(P(O)(OR')_2) and the subsequent reductive elimination to give RP(O)(OR')_2 with regeneration of a "PdL_2" species. The mechanism of the alpha-ketophosphonate metathesis reaction is also discussed.

各种 α-酮膦酸酯 RC(O)P(O)(OR')_2 在用 PdR_2L_2(R = Me, Et ; L = tertiary) 处理后催化脱羰得到膦酸酯 RP(O)(OR')_2磷化氢）、Pd(PPh_3)_4 或 Pd(PCy_3)_2。两种α-酮膦酸酯的交叉实验表明，在催化量的钯配合物(R^1C(O)P(O)存在下，α-酮膦酸酯的P-C键在脱羰之前发生复分解反应。 (OR^2)_2 + R^3C(O)p(O)(OR^4)_2 <双箭头> R^1C(O)P(O)(OR^4)_2 + R^3C(O)P(O)(OR^2)_2 反式 PdEt_2(PMe_3)_2 与 RC(O)P 的反应。 (O)(OR')_2 在甲苯回流条件下持续几分钟，得到黄色的 transPd(PMe_3)_2(C(O)R)(P(O)(OR')_2)分离的钯配合物在回流温度下在甲苯中产生相应的膦酸酯，并且还充当α-酮膦酸酯的脱羰和复分解反应的催化剂，整个催化脱羰反应由RC(O)的氧化加成组成。 P(O)(OR')_2 与 PdR_2L_2 或 PdL_4 生成的“PdL_2”物质形成 P-C 键，得到trans-PdL_2(C(O)R)(P(O)(OR')_2)，然后C(O)R配体脱羰得到PdL_2R(P(O)(OR')_2)和随后的还原消除得到 RP(O)(OR')_2 并再生“PdL_2”物质。还讨论了α-酮膦酸酯复分解反应的机理。

项目成果

Hiroshi Nakazawa: "Reaction of the lron Phosphorane Complex (n^5ーC_5H_5)(CO)_2Feー{P(0)(NEt_2)(OMe)}with Boron Trihalides.Preparation,Xーray Structure Analysis,and Reactivity of Iron ChloroーSubstituted Phosphorane Complex." Organometallic. 10. 766-770 (1991

Hiroshi Nakazawa：“铁磷烷络合物 (n^5ーC_5H_5)(CO)_2Feー{P(0)(NEt_2)(OMe)}与三卤化硼的反应。铁的制备、Xー射线结构分析和反应性氯取代的磷烷络合物。”有机金属。10. 766-770 (1991

Hiroshi Nakazawa, Hiroyuki Mosaka, Yoshihiko Kushi, and Hayami Yoneda: ""Reaction of Nickel(O) with alpha-Keto Phosphonates. Syntheses, Characterization, and X-ray Crystal Structure of (PPh_3)_2Ni(eta-(CO)RC(O)P(O)(OMe)_2)"" Organometallics. 9. 1958-1963

Hiroshi Nakazawa、Hiroyuki Mosaka、Yoshihiko Kushi 和 Hayami Yoneda：“镍 (O) 与 α-酮磷酸盐的反应。

Hiroshi Nakazawa, Yuko Matsuoka, Ikuko Nkagawa, k and Katsuhiko Miyoshi: ""Catalytic Carbon-Phosphorus Bond Activation by Palladium Complexes. Decarbonylation and metathesis Reactions of alpha-ketophosphonates and Isolation of Aroyl (phosphonato)-palladiu

Hiroshi Nakazawa、Yuko Matsuoka、Ikuko Nkakawa、k 和 Katsuhiko Miyoshi：“钯配合物催化碳磷键活化。”

Hiroshi Nakazawa: "Catalytic CarbonーPhosphorus Bond Activation by Palladium Comlexes.Decarbonylation and Metathesis Reactions of αーKetophosphonates and Isolation of Aroyl(phosphonato)palladium Complexe as Intermediates." Organometallics. 11. (1992)

Hiroshi Nakazawa：“钯络合物的催化碳-磷键活化。α-酮膦酸酯的脱羰和复分解反应以及芳酰基（膦酸）钯络合物作为有机金属中间体的分离。”（1992）。

Hiroshi Nakazawa: "Reaction of Nickel(O) with αーketo Phosphonates.Syntheses,Characterization,and Xーray Crystal Structure of (PPh_3)_2Ni(η^2ー(CO)RC(O)P(O)(OMe)_2" Organometallics. 9. 1958-1963 (1990)

Hiroshi Nakazawa：“镍(O)与αー酮磷酸盐的反应。(PPh_3)_2Ni(η^2ー(CO)RC(O)P(O)(OMe)的合成、表征和Xー射线晶体结构_2"有机金属学。9. 1958-1963 (1990)