Cyclopropanols, nucleophilic addition

Cyclopropanes, 1,2,3-trisubstituted, 205, 206 Cyclopropanols, nucleophilic addition cylization, 249-50 Cyclopropylcarbinyl-homoaUyl... 

Cyclopropanone ethyl hemiacetal is a molecule of considerable interest since its reactions appear to involve the formation of the labile cyclopropanone.7 It readily undergoes nucleophilic addition of Grignard reagents,4,5 azides,4 and amines5 to provide 1-substituted cyclopropanols in high yields. It has been reported that upon treatment with an equimolar amount of methylmagneslum iodide, the cyclopropanone ethyl hemiacetal is... 

The nucleophilic addition of organoaluminum reagent 60 to the magnesium salt 57 provided the homopropargylic cyclopropanol 61 in 50% yield. ... 

The 1,3-bond formation by electrolysis has been successfully applied for 1,3-disulfonates and 3-phenylthio-l-sulfonates as well as 1,3-dihalides. The electrolysis of a,a -dibromoketones in the presence of nucleophiles gives cyclopropanol derivatives resulting from the addition of the nucleophile to the carbonyl group . The electrolytic cyclization of 1,3-dibromides has been shown to be non-stereospecific. ... 

In the course of studies on cyclopropanone—)5-lactam conversions, Wasserman and coworkers developed a route to the nocardicins by taking advantage of the reactivity of primary amines with cyclopropanone. The unusual susceptibility of the carbonyl group of cyclopropanone to attack by nucleophiles is well exemplified in this synthesis which involves the addition of the highly hindered malonate derivative (156) to generate the cyclopropanol adduct (157). The hindered amine (156) was previously found to be completely unreactive as a nucleophile in a displacement reaction with dibromoester (158) in an attempt to form the azetidine carboxylate (159). The further conversion of the amino malonate adduct (157) to the -lactam through a nitrenium ion rearrangement is illustrated in Scheme 59. 

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