[Pd(C6H[C(O)CH2]-6-(OMe3)3-2,3,4)(N,N,N',N'-tetramethylethylenediamine)] | 172036-59-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: [Pd(C6H[C(O)CH2]-6-(OMe3)3-2,3,4)(N,N,N',N'-tetramethylethylenediamine)]
• CAS: 172036-59-8
• 化学式: C₁₇H₂₈N₂O₄Pd
• 分子量: 430.84
• InChiKey: NFHMLFIFPFRPBZ-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  [Pd(C6H(C(O)CH3)-6-(OMe3)3-2,3,4)Cl(N,N,N',N'-tetramethylethylenediamine)] 在 NaOCH₃ 作用下， 以 甲醇 为溶剂， 以87%的产率得到[Pd(C6H[C(O)CH2]-6-(OMe3)3-2,3,4)(N,N,N',N'-tetramethylethylenediamine)]
  参考文献：
  名称：

  Palladium-Assisted Formation of Carbon−Carbon Bonds. 9. Synthesis of (2-Alkenylaryl)- and Indenylpalladium Complexes

  摘要：

  (o-Formylaryl)palladium complexes. [Pd{C6H(CHO)-6-R-3-2,3,4)X(N-N)] [R = OMe; X = Cl; N-N = bpy (2,2'-bipyridine) (la), tmeda (N,N,N',N'-tetramethylethylenediamine) (Ib). R = H; X = Br; N-N = bpy (2a), tmeda (2b)] react with ylides PhCH=PPh3, pyCH=PPh3 (PY = 2-pyridyl), or ClCH=PPh3 to give the (o-alkenylaryl)palladium derivatives [Pd{C6HCH=CHPh-6-(OMe)(3)-2,3,4)Cl(N-N)] [N-N = bpy (3a), N-N = tmeda (3b)], [Pd{C6HCH= CHpy-6-(OMe)(3)-2,3,4}Cl(N-N)] [N-N = bpy (4)], [Pd{C6H(E-CH=CHCl)-6-(OMe)(3)-2,3,4}-Cl(tmeda)] (5), or [Pd(C6H4CH=CHPh-2)Br(N-N)] [N-N = bpy (6a), N-N = tmeda (6b)], The compounds 3a, 4, and 6a,b are obtained as mixtures off and Z isomers, whereas the formation of 3b and 5 is stereoselective (E isomer). The reaction of the (o-acetylaryl)palladium complexes [Pd{C6HC(O)Me-6-(OMe)(3)-2,3,4}Cl(tmeda)] (7) and [Pd{C6H4(C(O)Me)-2}Br(bpy)] (8) with bases results in the formation of the 3-palladaindan-1-ones [Pd(kappa (2)-{C6HC(O)CH2-6-(OMe)(3)-2,3,4})(tmeda)] (9) and [Pd(kappa (2)-{C6H4C(O)CH2-2)(bpy)] (10). Complexes 3b and 6a,b react with alkynes-RC=CR' to give indenylpalladium complexes [Pd{eta -C9HBn-1-R-2-R'-3-(OMe)(3)-5,6,7}(tmeda)]TfO [Bn = benzyl, TfO = CF3SO3, R = R' = Me(11); R = C(O)Me, R' = H (12)] and [Pd{eta -C9H4Bn-1-R-2-R'-3}(N-N)]TfO [R = R' = H, N-N = bpy (13a), tmeda (13b); R = R' = Me, N-N = bpy (14a), tmeda (14b); R = R' = Et, N-N = bpy (15a), tmeda (15b); R = R' = Ph, N-N bpy (16a), tmeda (16b); R = Ph, R' = H and R = H, R' = Ph, N-N = bpy (17a); R = H, R' = Ph, N-N = tmeda (17b); R = Ph, R' = Me, N-N = bpy (18a), N-N = tmeda (18b)]. Complex 3b reacts with Me2C=C=CH2, CS2, or MeN=C=S to give [Pd(eta (3)-CMe2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4}CH2)(tmeda)]TfO (19), [Pd(S2C{C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (20), or [Pd(SC(NMe)(C6H(E-CH=CHPh)-6-(OMe)(3)-2,3,4})(tmeda)]TfO (21). The crystal structures of 12, 17b, and 18a have been determined; the hapticities of the indenyl five-membered rings are intermediate between eta (3) and eta (5).

  DOI：

  10.1021/om000370w

文献信息

• The first ligand-assisted stereoselective Wittig reactions. Synthesis and crystal structure of the 3-palladaindan-1-one, [Pd{C6H[C(O)CH2]-6-(OMe)3-2,3,4}(Me2NCH2CH2NMe2)]
  作者：Jos� Vicente、Jos�-Antonio Abad、Ralph Bergs、Peter G. Jones、Delia Bautista

  DOI：10.1039/dt9950003093

  日期：——

  Reactions of [Pd(R(H))Cl(L-L)] [R(H) = C6H(CHO)-6-(OMe)(3)-2,3,4] with Ph(3)P=CHR (R = Ph or 2-pyridyl) gave mixtures of the isomeric compounds [Pd(E-R')Cl(L-L)] and [Pd(Z-R')Cl(L-L)] [R' = C6H(CH=CHPh)-6-(OMe)(3)-2,3,4 or C6HCH=CH(C5H5N-2)}-6-(OMe)(3)-2,3,4] when L-L = 2,2'-bipyridine or only the corresponding E isomers when L-L = N,N,N',N'-tetramethylethylenediamine; however, the complex [Pd(R(Me))C\(tmeda)] [R(Me) = C6HC(O)Me}-6-(OMe)(3)-2,3,4] reacts with Ph(3)P=CHPh to give [PdC6H[C(O)CH2]-6-(OMe)(3)-2,3,4}(tmeda)].