| 123863-25-2

• CAS: 123863-25-2
• 化学式: C₂₄H₂₁CrNO₄
• 分子量: 439.431
• InChiKey: RHNBAKYNBIUDAP-WUDICJIASA-N

反应信息

• 作为产物：
  描述：

  Carbon monoxide;1-pyrrolidin-1-ylethylidenechromium 、 二苯基乙炔 以 苯 为溶剂， 以32%的产率得到
  参考文献：
  名称：

  炔烃插入时铬的氨基碳烯配合物的新反应：乙烯酮中间体的脱氧重排。四氢吲哚嗪复合物的形成和X射线结构

  摘要：

  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。

  DOI：

  10.1039/c39900001238

文献信息

• Unexpected ring opening of cycloaminocarbene complexes of chromium upon alkyne insertion reactions
  作者：H. Rudler、A. Parlier、R. Yefsah、B. Denise、J.C. Daran、J. Vaissermann、C. Knobler

  DOI：10.1016/0022-328x(88)87082-7

  日期：1988.12

  Aminocarbenechromium complexes of the general structure (CO)5CrC(R)N-(CH2)nXCH2 (n = 0, X  CH2; n = 1, X  CH2; n = 1, X  CHCH; n = 2, X  molecules of alkyne and one molecule of CO, and CN bond cleavage, new polycyclic heterocycles. The reactions of the pyrroline-, the tetrahydropyridine-, the pyrrolidine- and the methylaziridine-substituted complexes are mainly considered, and the results of

  的一般结构的复合物Aminocarbenechromium（CO）5 CrC（R）N-（CH 2）Ñ XCH 2（Ñ = 0，XCH 2 ; Ñ = 1，XCH 2 ; Ñ = 1，X CH = CH；n = 2，炔烃的X分子和一个CO分子，以及C bondN键断裂，形成新的多环杂环，吡咯啉-，四氢吡啶-，吡咯烷-和甲基氮丙啶取代的配合物反应主要考虑了这些因素，并给出了新产品的X射线结构研究结果，并讨论了1,5偶极重排的机理。
• 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.