ISSN:
0009-2940
Keywords:
Cyclobutanimines via carbene complexes
;
10-Iminotricyclo[5.3.0.02,9]deca-3,5-dienes
;
(Cycloheptatrien-1-ylmethyl)carbene complexes of chromium and tungsten
;
Ketenimine complexes, [2 + 2] cycloadditions with alkenes
;
Ketene complexes, [2 + 2] cycloadditions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Organic Syntheses via Transition Metal Complexes, 59[1]. - Cyclobutanimines from Carbenechromium or -tungsten Complexes, Isocyanides, and Alkenes by [2 + 2]-Cycloaddition Reactions of Ketenimine Complexes; Ligand Disengagement with Pyridine10-Iminotricyclo[5.3.0.02,9]deca-3,5-diene complexes syn/anti-4 are obtained in yields higher than 90% by the addition of isocyanides RNC 2 [R = c-C6H11 (a), CH3 (b)] to (cycloheptatrien-1-ylmethyl)carbene complexes LnM=C(OEt)CH2(C7H7) 1 [LnM = Cr(CO)5 (a), W(CO)5 (b)]. The reactions involve an intermediate formation of ketenimine complexes LnM[RN=C=C(OEt)CH2C7H7] 3 by the insertion of 2 into the M=C bonds of 1. Complexes 3 isomerize to give the cyclo-butanimines 4 by an intramolecular [2s + 2a]-cycloaddition reaction of the ketenimine to the alkene unit. The structure of anti-4c has been determined by a crystal structure analysis. Complexes 4 react with pyridine by the fragmentation of the four-membered ring to yield a tetrahydroazulen-1-imine 6 which was hydrolyzed to the corresponding ketone 7;7 is also obtained along an independent route by the photolysis of 1a in the presence of carbon monoxide. The first isolated product of the latter reaction is the tricyclo[5.3.0.02,9]deca-3,5-dienone 9, which presumably is formed via an intermediate ketene complex N and the tricyclic ketone O; 9 on warming with pyridine rearranges to 7.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250718
