trichloro{2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III) | 131864-84-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: trichloro{2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III)
• 英文别名: 2-[6-(4,4-dimethyl-5H-1,3-oxazol-2-yl)pyridin-2-yl]-4,4-dimethyl-5H-1,3-oxazole;trichlororhodium
• CAS: 131864-84-1
• 化学式: C₁₅H₁₉Cl₃N₃O₂Rh
• 分子量: 482.599
• InChiKey: CZSKFKLVBJGYDB-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  56.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  trichloro{2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III) 在 三甲基铝 作用下， 以 二氯甲烷 为溶剂， 以86%的产率得到cis-dichloro(methyl){2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III)
  参考文献：
  名称：

  烷基氯与氯双（环辛烯）铑（I）和双（恶唑啉基）吡啶配体的氧化加成反应：稳定的（氯甲基）铑（III）配合物的形成及其反应

  摘要：

  Dichloromethane and chloroform readily react with chlorobis(cyclooctene)rhodium(I) (1) and 2,6-bis-(4,4-dimethyloxazolin-2-yl)pyridine, dm-pybox, at room temperature to give the stable (chloromethyl)-rhodium(III) complex 2 and (dichloromethyl)rhodium(III) complex 4, respectively. Several organic halides also react with 1 to give the corresponding substituted alkylrhodium(III) complexes. Some reactions of the chloromethyl complexes were also demonstrated. Decomposition of 2 and 3 in methanol at 100-130-degrees-C gave the methylrhodium(III) complex, in which the origin of the methyl group can be traced to be methanol.

  DOI：

  10.1021/om00054a036
• 作为产物：
  描述：

  cis-dichloro(methyl){2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III) 以 二氯甲烷 为溶剂， 以68%的产率得到trichloro{2,6-bis(4,4-dimethyloxazolin-2-yl)pyridine}rhodium(III)
  参考文献：
  名称：

  双（恶唑啉基）吡啶鎓氯化铑（III）与三甲基铝的甲基化

  摘要：

  用三甲基铝处理三氯化双（恶唑啉基）吡啶鎓铑（III）（1），立体选择性地得到相应的稳定的甲基铑络合物，单轴向甲基络合物（2）和顺式-二甲基络合物（3）。还发现在甲基化过程中，在轴向和赤道位置处的甲基争夺，伴随着铑金属上的甲基与铝原子上的甲基之间的相互交换。

  DOI：

  10.1016/0022-328x(92)80120-m

文献信息

• Highly enantioselective hydrosilylation of ketones with chiral and C2-symmetrical bis(oxazolinyl)pyridine-rhodium catalysts
  作者：Hisao Nishiyama、Manabu Kondo、Takashi Nakamura、Kenji Itoh

  DOI：10.1021/om00048a029

  日期：1991.2

  Chiral and C2-symmetrical 2,6-bis(4'-R-oxazolin-2'-yl)pyridines (pybox, 1a-e, R = i-Pr, sec-Bu, t-Bu, Et, and Ph) have been newly designed and synthesized from the corresponding optically active beta-amino alcohols and pyridine-2,6-dicarboxylic acid as auxiliaries for metal-catalyzed reactions. We have found that the trivalent rhodium-pybox complexes 2a-e can act as catalysts for asymmetric reduction of ketones with diphenylsilane. The (S,S)-ip-pybox-rhodium complex 2a (1 mol % with respect to the ketone) with the aid of AgBF4 has exhibited an extremely high level of enantioselectivity for the reduction of acetophenone derivatives, above 90% ee on the average. Under the same reaction conditions, we have attained complete selection of the prochiral face of 1-tetralone in 99% ee. Several other ketones also have relatively higher results e.g. 95% ee for ethyl levulinate, 94% ee for 1-acetylnaphthalene, and 63% ee for 2-octanone. We have examined alpha,beta-unsaturated ketones, resulting in an exclusive 1,2-reduction for benzalacetone, beta-ionone, and chalcone but in lower enantioselection. We have also examined the effect of the substituents on the pybox ligands in the reduction of acetophenone and ethyl levulinate. In the mixed-ligand experiments a facile ligand-exchange reaction between the coordinating pybox and the free pybox ligand in the reaction media was observed, resulting in complete linearity of the enantiomeric excess between the product and the catalytic system.