CREATION AND CATALYTIC PROPERTIES OF ORGANOTRANSITION METAL COMPLEXES BEARING PHOSPHAALKENE LIGANDS

含磷烯配体有机过渡金属配合物的制备及其催化性能

• 批准号: 15350060
• 负责人: OZAWA Fumiyuki
• 金额: $ 9.15万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350060/
• 关键词: Phosphaalkene Ligands; Palladium Complexes; Rhodium Complexes; Ruthenium Complexes; Dehydrative Allylation Catalyst; Conjugate Addition Catalyst; Cross-Coupling Catalyst; Hydrosilylation Catalyst; ジホスフィニデンシクロブテン; 脱水環化触媒; π共役分子; ヒロリドパラジウム錯体; 脱ア

(1)Electronic and steric properties of 1,2-diaryl-3,4-bis(2,4,6-tri-t-butylphenylphosphinidene)cyclobutene ligands [aryl=4-methoxyphenyl (DPCB-OMe) ; phenyl (DPCB) ; 4-trifluoromethylphenyl (DPCB-CF_3)] have been investigated using their methylplatinum(II) and palladium(II) complexes. It has been found that DPCB-Y ligands possess intermediate magnitude of σ-donating ability between common diimine and diphosphine ligands, but be much stronger π-acceptors than the other supporting ligands.(2)The mechanism of dehydrative condensation of allylic alcohols and aniline (i.e. N-allylation of aniline) catalyzed by palladium DPCB-OMe complex has been examined by model studies of possible intermediates as well as kinetic investigations. A novel process involving a hydridopalladium intermediate has been proposed for C-O bond cleavage of allylic alcohol to give (π-allyl)palladium complexes.(3)(π-Allyl)palladium triflate bearing DPCB-OMe ligand efficiently catalyzes deallylation of a variety of ally … More l ethers in aniline to give corresponding alcohols in high yields under mild conditions. The same complex serves as a highly active catalyst for cyclodehydration of cis-2-butene-1,4-diol with active methylene compounds to give 2-vinyl-2,3-dihydrofurans.(4)Cationic complexes of the formula [Pd(MeCN)_2(DPCB-Y)](OTf)_2 and [Rh(MeCN)_2(DPCB-Y)](OTf) have been prepared. The former shows high catalytic activity towards conjugate addition of benzyl carbamate to α,β-unsaturated ketones.(5)Palladium or copper complexes bearing DPCB catalyze cross-coupling of aryl halides with anilines, organotin reagents, or zinc cyanide.(6)Dichlororuthenium complex bearing DPCB-OMe ligand catalyzes highly stereoselective hydrosilylation of diethynylarenes with HSiMe_2Ph to give (Z,Z)-bis(2-silylethenyl)arenes. Treatment of the hydrosilylation products with NBS causes bromodesilylation in a stereospecific manner, giving (Z,Z)-bis(2-bromoethenyl)arenes with high geometrical purities (>98%). (Z,Z)-Bis(2-bromoethenyl)benzenes thus obtained have been applied to the synthesis of geometrically pure all-cis poly(phenylene vinylene)s (PPVs), which are synthesized by Suzuki-Miyaura-type polycondensation with 2,5-dioctyloxy-1,4-benzenediboronic acid. The all-cis PPVs undergo one-way photoisomerization to the corresponding trans-PPVs both in solution and in the solid. This phenomenon is applied to direct microscale patterning of PPVs onto a quartz substrate. Less

（1）用1，2-二芳基-3，4-双（2，4，6-三叔丁基苯基膦）环丁烯配体[芳基=4-甲氧基苯基（DPCB-OMe）;苯基（DCB）; 4-三氟甲基苯基（DPCB-CF_3）]的甲基铂（II）和钯（II）配合物研究了它们的电子和空间性质。结果表明，DPCB-Y配体的σ-供电子能力介于一般的双亚胺和双膦配体之间，但其π-受体能力远强于其它的配体。（2）通过对可能的中间体的模型研究和动力学研究，探讨了钯-DPCB-OMe配合物催化烯丙醇与苯胺脱水缩合反应（即苯胺的N-烯丙基化反应）的机理。本文提出了一种以烯丙醇为原料，以钯为中间体，通过C-O键裂解制备（π-烯丙基）钯配合物的新方法。(3)(含DPCB-OMe配体的三氟甲磺酸（π-烯丙基）钯催化剂能有效地催化多种烯丙基的脱烯丙基化反应 ...更多信息 在温和的条件下，以较高的产率得到相应的醇。该配合物可作为顺式-2-丁烯-1，4-二醇与活性亚甲基化合物环化脱水生成2-乙烯基-2，3-二氢呋喃的高活性催化剂。（4）合成了配合物[Pd（MeCN）_2（DPCB-Y）]（OTf）_2和[Rh（MeCN）_2（DPCB-Y）]（OTf）。前者对氨基甲酸苄酯与α，β-不饱和酮的共轭加成反应表现出较高的催化活性。（5）带有DPCB的钯或铜络合物催化芳基卤化物与苯胺、有机锡试剂或氰化锌的交叉偶联。（6）含DPCB-OMe配体的二氯钌配合物催化二乙炔基芳烃与HSiMe_2Ph的高立体选择性硅氢加成反应，合成了（Z，Z）-双（2-硅基乙烯基）芳烃。用NBS处理氢化硅烷化产物以立体定向方式引起溴脱甲硅烷基化，得到具有高几何纯度（>98%）的（Z，Z）-双（2-溴乙烯基）芳烃。将所得到的（Z，Z）-双（2-溴乙烯基）苯用于合成几何纯的全顺式聚对苯乙炔（PPV），并与2，5-二辛氧基-1，4-苯二硼酸通过Suzuki-Miyaura型缩聚反应合成了PPV。全顺式PPV在溶液和固体中均发生单向光异构化，生成相应的反式PPV。这种现象被应用于将PPV直接微尺度图案化到石英衬底上。少

项目成果

Catalytic C-O Bond Cleavage of Allylic Alcohols using Diphosphinidenecyclobutene-coordinated Palladium Complexes. Mechanistic Study

使用二膦亚基环丁烯配位钯配合物催化烯丙醇的 C-O 键断裂。

• 发表时间: 2004
• 期刊: Organometallics 23・8
• 作者: F;Ozawa;H;Katayama;K.Toyota;M.Yoshifuji;R.S.Jensen;長尾将人;A.S.Gajare;片山博之;小澤文幸;小澤文幸
• 通讯作者: 小澤文幸

Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides

• DOI: 10.1039/b408232j
• 发表时间: 2004-01-01
• 期刊: CHEMICAL COMMUNICATIONS
• 影响因子: 4.9
• 作者: Gajare, AS;Toyota, K;Ozawa, F
• 通讯作者: Ozawa, F

Facile and Selective Deallylation of Allylic Compounds using Diphosphinidenecyclobutene-coordinated Palladium Catalysts

使用二膦亚基环丁烯配位钯催化剂轻松选择性地对烯丙基化合物进行脱烯丙基化

• 发表时间: 2004
• 期刊: J. Org. Chem. 69(13)
• 作者: H.Murakami;T.Minami;F Ozawa
• 通讯作者: F Ozawa

Stereoselective Synthesis of cis- and trans-Oligo(phenylenevinylene)s via Palladium-Catalyzed Cross-Coupling Reactions

通过钯催化交叉偶联反应立体选择性合成顺式和反式寡聚（亚苯基亚乙烯基）

• 发表时间: 2006
• 期刊: Journal of Organic Chemistry 71
• 作者: Katayama;Hiroyuki
• 通讯作者: Hiroyuki

sp^2混成リン配位子をもつ特異な遷移金属錯体触媒

独特的具有sp^2杂化磷配体的过渡金属配合物催化剂

• 发表时间: 2005
• 期刊: 触媒 47・7
• 作者: H.Tsukamoto;M.Sato;Y.Kondo;Akitake Nakamura;Anil S.Gajare;Subaru Kawasaki;Subaru Kawasaki;Akitake Nakamura;Subaru Kawasaki;Rader S.Jensen;小澤文幸
• 通讯作者: 小澤文幸