carbon monoxide;chromium;3-methyl-1,2-diphenyl-5,6,7,8-tetrahydroindolizine | 131374-62-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: carbon monoxide;chromium;3-methyl-1,2-diphenyl-5,6,7,8-tetrahydroindolizine
• CAS: 131374-62-4
• 化学式: C₂₄H₂₁CrNO₃
• 分子量: 423.432
• InChiKey: UDPQNOSIXSDYAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.35
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  二苯基乙炔 、 Carbon monoxide;1-pyrrolidin-1-ylethylidenechromium 生成 carbon monoxide;chromium;3-methyl-1,2-diphenyl-5,6,7,8-tetrahydroindolizine
  参考文献：
  名称：

  DENISE, B.;GOUMONT, R.;PARLIER, A.;RUDLER, H.;DARAN, J. C.;VAISSERMANN, J+, J. CHEM. SOC. CHEM. COMMUN.,(1990) N8, C. 1238-1240

  摘要：

  DOI：

文献信息

• A new reaction of aminocarbene complexes of chromium upon alkyne insertions: deoxygenation rearrangement of ketene intermediates. Formation and X-ray structure of a tetrahydroindolizine complex
  作者：B. Denise、R. Goumont、A. Parlier、H. Rudler、J. C. Daran、J. Vaissermann

  DOI：10.1039/c39900001238

  日期：——

  Aminocarbene complexes (1) of chromium bearing suitable substituents on nitrogen react with alkynes to give, besides the expected heterocyclic compounds (5) and (6) originating from cascade alkyne–CO insertion–rearrangement reactions, deoxygenation–rearrangement products (8) of ketene intermediates, whereas when nitrogen bears substituents of low migratory aptitude, ketene complexes (4) and their derivatives

  氮上带有合适取代基的铬的氨基碳烯配合物（1）与炔烃反应，除产生预期的杂环化合物（5）和（6）外，还可以从级联炔烃-CO插入-重排反应，脱氧-乙烯酮的重排产物（8）中间体，而当氮带有低迁移性的取代基时，可以分离烯酮配合物（4）及其衍生物（7）并通过光谱法或X射线晶体学对其进行充分表征。
• Reaction of Aminocarbene Complexes of Chromium with Alkynes. 5. Influence of the Ring Size on the Product Distribution. Formation of Pyrroles from Pyrrolidine and Its Derivative-Substituted Carbene Complexes
  作者：Andree Parlier、Michele Rudler、Henri Rudler、Regis Goumont、Jean-Claude Daran、Jacqueline Vaissermann

  DOI：10.1021/om00006a024

  日期：1995.6

  A series of aminocarbene complexes of chromium derived from piperidine (1), hexa- and heptamethyleneimine (4) and (8), pyrrolidine (13a-d, R(1) = Me, H, Ph, thienyl), perhydroindole (21), thiazolidine (24a,b, R(1) = Me, Ph), pyrroline (30a,b), and azetidine (33a-e and 36) have been synthesized and subjected to alkyne insertion reactions. Aminocarbene complex 24a-E has been fully characterized by X-ray structure analysis. Crystal data for 24a-E: C10H9O5NSCr, monoclinic, space group P2(1)/n, a = 8.3011(9) Angstrom, b = 11.949(1) Angstrom, c = 13.101(2) Angstrom, beta = 95.74(1)degrees, V = 1293(1) Angstrom(3), d(calcd) = 1.41 g cm(-3), Z = 4. Whereas complex 1 reacted with diphenylacetylene to give first the ylide complex 2, the thermolysis of which led to the bridgehead lactam 3, complexes 4, and 8 gave directly the expected bridgehead lactams 6 and 11. The structure of 3 has been determined by X-ray diffraction. Crystal data for 3: C27H25ON, monoclinic, space group P2(1)/c, a = 10.080(4) Angstrom, b = 11.727(3) Angstrom, c 18.014(6) Angstrom, beta = 102.40(3)degrees, V = 2080(14) Angstrom(3), d(calcd) = 1.21 g cm(-3), Z = 4. In contrast to 1, 4, and 8, all of the new carbene complexes derived from five-membered cycloamines except 24b gave pyrrole derivatives as the result of the alkyne/CO insertion followed by migration of an alkyl chain from nitrogen to the carbon atom of the inserted carbonyl group and loss of its oxygen atom. The structures of 14a, the Cr(CO)(3) complex of 15a, and 22 could be unambiguously established by X-ray crystallography. Crystal data for 15: C24H21O3NCr, triclinic, space group P1, a = 6.918(1) Angstrom, b = 10.057(1) Angstrom, c = 15.193(2) Angstrom, alpha = 72.410(9)degrees, beta = 84.99(1)degrees, gamma = 84.66(3)degrees, V = 1001(3) Angstrom(3), d(calcd) = 1.40 g cm(-3), Z = 2. For 22: C24H25N, monoclinic, space group P2(1)/n, a = 11.119(3) Angstrom, b = 10.682(2) Angstrom, c = 15.428(3) Angstrom, beta = 102.23(2)degrees, V = 1791(7) Angstrom(3), d(calcd) = 1.21 g cm(-3), Z = 4. Besides these pyrroles, the expected bridgehead lactams 17a-d were isolated from 13a-d together with the lactone complex 18 in the case of 13b. Crystal data for 18: C19H12O5Cr, orthorhombic, space group Pc2(1)/b, a = 10.356(1) Angstrom, b = 12.366(5) Angstrom, c = 12.529(2) Angstrom, V = 1604.4(8) Angstrom(3), d(calcd) = 1.54 g cm(-3), Z = 4. However, 24b gave as the major insertion product the aminofuran 26, and pyrroline-derived carbene complexes 30a,b gave lactams 32a,b and trace amounts of pyrroles 31a,b. Only trace amounts of pyrroles were detected starting from carbene complexes derived from azetidine (33a-e) and 36, which gave mainly the lactams 35a,d and 37. Mechanisms for these new transformations of aminocarbene complexes of chromium based on the behavior of the Stevens-type acyl-stabilized N-ylides will be suggested.