36692-55-4Relevant academic research and scientific papers
Organic Syntheses via Transition Metal Complexes, 43. - 2-Azaallenyl Chromium Complexes; Insertion of 1-Aminopropyne into M=C and C=O Bonds; Intramolecular Cyclopropanation and Cycloaddition with Formation of a 1,3-Diaminoindene
Aumann, Rudolf,Heinen, Heinrich,Krueger, Carl,Betz, Peter
, p. 605 - 610 (2007/10/02)
The 2-azaallenyl complex LnM--C(Ph)=N+=C(Ph)OCO-Ph 3 nM=Cr(CO)5> adds to the 1-aminopropyne Et2N-CC-CH3 (4) to give the aminocarbene complexes LnM=C(NEt2)-C(CH3)=C(Ph)-N(COPh)2 and LnM=C(NEt2)-C(CH3)=C(Ph)-NH(COPh) (by insertion of 4 into the M=C bond of 3) as well as a 1,3-diaminoindene 6 (by cycloaddition).An iminocarbene complex LnM=C(Ph)-N=C(Ph)-O-C(Ph)=C(CH3)-CONEt2 (7) is formed as a further product (by insertion of 4 into the C=O bond of 3).The latter type of reaction can also be applied to metal-free carbonyl compounds: thus phthalic anhydride reacts smoothly with 4 to give a γ-lactone 12 and a 1,3-indanedione 13 by insertion of 4 into a C=O and C-O bond, respectively.The thermolysis of the iminocarbene complex 7 yields a cyclopropane derivative 14 by an intramolecular attack of the carbene carbon at the (O)C=C bond.The structure of 14 has been determined by a crystal structure analysis.On thermolysis of 3 a triphenyloxazole 15 is obtained.The mechanisms of these reactions are discussed.
