Dipole aliphatic nitriles

If the cyano group is attached to a non-conjugated alicyclic ring, as in the aliphatic nitriles (54-59) also collated in Table then the dipole moment... 

The dipole moment (DM) showed a poor correlation (r < 0.49) for alcohols, all aromatics, and all halogenated aliphatics however, for small molecules (two carbons), dipole moment correlations were significant for halogenated aliphatics and nitriles, as shown in Equation (5.15). 

The first report of the reaction of 2//-l-benzopyran (139) with various 1,3-dipoles has appeared/ Good yields of single cycloaddition products (140) were obtained upon reaction with nitrile-imines, whereas nitrile oxides gave 1 1 mixtures of the regioisomers (141) and (142), The reactions with diazomethane gave rather inconclusive results, and phenyl azide and diphenyl nitrone failed to react. Similar types of reactions have been carried out using a variety of enones in which the overall conclusion appears to be that simple aliphatic or alicyclic enones produce mixtures of regioisomers upon reaction with nitrile oxides and nitrile imines whereas enones of the chalcone type show only one product. Experts in FMO theory will probably declare these results... 

Sibi et al. reported that substoichiometric chiral Mg(II) complexes catalyzed regio- and enantioselective nitrile oxide cycloadditions to electron-deficient alkenes (Scheme 4.8) [6]. For an achiral template, bulky pyrazolidinone (20) was essential for high regio- and enantioselectivity in (22) and (23), while oxazolidinone crotonate and 3,5-dimethylpyrazole gave the adducts, but with poor results. In particular, mesityl nitrile oxide (21), a stable dipole, was chosen as the reagent due to steric interactions of that group with either a bulky achiral template and/or a bulky Lewis acid center. Aliphatic (t-Bu and i-Bu) nitrile oxides also provided cycloaddition... 

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