| 143841-27-4

• CAS: 143841-27-4
• 化学式: C₂₁H₂₁CrNO₄
• 分子量: 403.398
• InChiKey: MSUDDYNBXAYQRH-XIYRCBLHSA-N

反应信息

• 作为产物：
  描述：

  pentacarbonylchromium(N(CH2)5)(CH2)3CC(phenyl) 以 苯 为溶剂， 以40%的产率得到
  参考文献：
  名称：

  Reaction of aminocarbene complexes of chromium with alkynes. 1. Formation and rearrangement of ketene and nitrogen ylide complexes

  摘要：

  The title reactions of chromium-containing carbene complexes (CO)5Cr=C(R1)N(R2R3) (R1 = H, Me, Ph; R2 = Me; R3 = Me, C3H5, CH2C3H5; R2R3 = (CH2)5) 8 and (CO)5Cr=C[(CH2)3C=CPh]N(R1R2) (R1 = R2 = Me; R1R2 = (CH2)5; R1R2 = (CH2)4) 9, bearing alkyl groups of low migratory aptitude on nitrogen, have been examined. In contrast to complexes in which nitrogen bears either an alkyl and an allyl or a benzyl group or is part of a strained cycle, which give heterocycles upon alkyne/CO insertions followed by nitrogen-to-carbon migrations (e.g., 1 --> 7), complexes 8 and 9 lead to stable nitrogen ylides, which could be fully characterized by X-ray crystallography in the case of 8a and 9a. Moreover, in the case of complexes of the general structure 9, ketene precursors of the ylides could either be detected (R1 = Me; R2 = CH2Ph) or isolated and characterized (R2R3 = (CH2)5). The new ylide complexes undergo, upon moderate heating, Stevens-type rearrangements to the expected heterocyclic compounds as a result of nitrogen-to-carbon migrations of various alkyl groups, and upon treatment with dimethyldioxirane, they undergo oxidation to lactone complexes.

  DOI：

  10.1021/ja00047a018