Trimethyl phosphite-Copper iodide

Dimethyl (cyclohex-2-enyl)malonate (6%) and tetrakis(methoxycarbonyl)ethene (12%) were also formed. With trimethyl phosphite/ copper(I) iodide, the yields were 74, 6 and 12%. 

Decomposition of diethyl diazomalonate (1). Decomposition of (1) at 50° in ethanol catalyzed by trimethyl phosphite—copper(l) iodide results in forma-... 

Trimethyl phosphite copper(I) iodide benzoyl peroxide... 

A soln. of dimethyl diazomalonate and cycloheptene added at 6 drops per min. to a refluxing soln. of trimethyl phosphite copper(I) iodide and benzoyl peroxide in cycloheptene, and the product isolated after 24 hrs. reflux -> 8,8-dimethoxy-carbonylbicyclo[5.1.0]octane. Y 80%. F. e., prepn. and reactions of diazomalonic esters, review, s. B.W. Peace and D. S. Wulfman, Synthesis 1973, 137 with an azomethine-type CuH-complex as catalyst cf. R. Noyori et al., Chem. Lett. 1973, 3. 

Allylation of all these species is apparently less selective (Scheme 69, entry a), and among the various thioacetals tested 1,3-dithianes proved to be the ones which lead to the highest 0 7 The use of HMPA as a cosolvent was shown to have no effect on the regioselectivity of the allylation. However, both exclusive 7-allylation and 7-methylation have been achieved by performing the reaction in the presence of copper(I) iodide-trimethyl phosphite complex (Scheme 69, entries a-e). The reaction is best achieved with allylic chlorides, bromides and phosphate esters and does not occur with acetates, although these compounds usually react with cuprates. In all cases where isomers could be formed with respect to the electrophile, the ratio of 5n2 5n2 products was found to be greater than 0.67 (Scheme 69, entries b-e).- Related reactions have already been described with allylic sulfides (Scheme 27, see Section 1.3.2.2.4). 62.iM... 

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