4-Chloro-5-(dimethylamino)pent-3-en-1-ol;chloropalladium(1+);2-isocyano-2-methylpropane | 643056-81-9

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-Chloro-5-(dimethylamino)pent-3-en-1-ol;chloropalladium(1+);2-isocyano-2-methylpropane
• CAS: 643056-81-9
• 化学式: C₁₂H₂₂Cl₂N₂OPd
• 分子量: 387.645
• InChiKey: XWPZUSKNRPOUQU-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.25
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  27.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  5-(二甲氨基)戊-3-炔-1-醇 以 甲醇 、 氘代氯仿 为溶剂， 生成 4-Chloro-5-(dimethylamino)pent-3-en-1-ol;chloropalladium(1+);2-isocyano-2-methylpropane
  参考文献：
  名称：

  The retro-chloropalladation reaction of heterosubstituted alkynes

  摘要：

  The bridge-splitting reaction of dimeric palladacycles of the type {Pd[kappa(1)-C, kappa(1)-N-C(R) = C(Cl)CH2NMe2](mu-Cl)}(2) (R = Ph, Me, CH2CH2OH), derived from the chloropalladation of propargyl amines (RCdropCCH(2)NMe(2)), with pyridine (Py), triphenylphosphine (PPh3) and tert-butytisonitrile ((BuNC)-Bu-t) affords the monomeric compounds [PdC(R)=CCH2NMe2(Cl)L] (L = Py, PPh3, (BuNC)-Bu-t). These monomeric compounds are not stable in solution and undergo retro-chloropalladation reactions yielding the propargyl amines and [PdCl(L)-mu-Cl](2). This process is strongly dependent upon the nature of the incoming nucleophile (L), the R group on the metallated ligand and the temperature. The retro-halopalladation reaction is almost instantaneous in the case of the reaction of the bromo derivative [PdC(Ph)=C(Br)CH2NMe2-mu-Br](2) and pyridine at room temperature. These results can be rationalized in terms of the stability of the Pd-C bond of the intermediate monomeric compound [PdC(R)=C(X)CH2NMe2(X)L], that is directly related to the nature of its substituents R (Ph, Me and CH2CH2OH), of ligands which are both cis and trans to it (Py, (CNBu)-Bu-t, PPh3, Cl and Br) and the temperature. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00324-3