| 165964-69-2

• CAS: 165964-69-2
• 化学式: C₃₀H₃₁ClO₃P₂Pt
• 分子量: 732.055
• InChiKey: VNFXGRJGPADYIN-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  二苯基氯化膦 、 (二苯基膦基)甲醇 以 二氯甲烷 、 二氯甲烷-D2 为溶剂， 生成
  参考文献：
  名称：

  Reactions of Diazo Carbonyls with [PtX(CH3)(chiral diphosphine)] (X = Cl, Br, I): Chemoselectivity and Diastereoselectivity of Pt-C and Pt-X Carbene Insertion

  摘要：

  In polar solvents (e.g. MeCN), ethyl diazoacetate reacts with [PtXMe(S,S-diop)], where X = Cl, Pr, I, to give the corresponding [PtX(CHMeCO(2)Et)(S,S-diop)] as a 2:1 mixture of diastereoisomers in high yields. The major diastereoisomer of [PtCl(CHMeCO(2)Et)(S,S-diop)] is readily separated in crystalline form, and its crystal structure reveals that the configuration at the alpha-carbon is R; it is configurationally stable in CDCl3 for at least 14 days. The factors that influence the diastereoselectivity have been examined by comparing (by P-31 NMR spectroscopy) the ratio of diastereoisomers formed in the reactions between [PtXMe(diphos*)] and N(2)CHCOR: X = Cl, Pr, I; diphos* = S,S-diop, R,R-diop, S,S-skewphos, S,S-chiraphos; R = OEt, O(l-menthyl), Ph. In MeCN, the diastereoselectivity is independent of halogen but is a sensitive function of the chiral diphosphine and diazo carbonyl, though no systematic correlations have been divined. In solvents of lower polarity (e.g. CH2Cl2), diazo carbonyls react with [PtXMe(diphos*)] to give the products derived from Pt-X insertion as well. as Pt-C insertion. When C6H6 is used as the solvent, the compounds [PtMe(CHICOR)(S,S-diop)], where R = Oft, O(l-menthyl), Ph, are formed in high yields and have been isolated. Redissolving these compounds in MeCN did not lead to isomerization to the Pt-C insertion species [PtI(CHMeCOR)(S,S-diop)]. Several trends have been found relating the extent of Pt-C insertion to the nature of the solvent and the structure of the reagents: the proportion of Pt-C insertion increases with (i) increasing polarity of the solvent (C6H6 < CHCl3 < CH2 . Cl-2 < (CH3)(2)SO), (ii) increasing nucleofugacity of the halogen (I < Pr < Cl), (iii) decreasing bite angle of the diphosphine (diop < chiraphos, skewphos), and (iv) diazo ketone < diazo ester. A mechanism which is consistent with these observations is discussed. Many of the compounds discussed here have been observed in solution only by P-31 NMR, but representative species have been isolated and fully characterized by a combination of elemental analysis, IR spectroscopy, and H-1, C-13, P-31, and Pt-195 NMR spectroscopy.

  DOI：

  10.1021/om00007a019