2-Phenylcyclopropane-1,3- 2-1 -carbonitril

NHase from Rhodococcus. sp. AJ270 was isolated, purified, and applied to the enantiose-lective transformation of a series of cyclopropane carbonitriles. Amides with moderate ee were isolated from conversion of many of the cyclopropane substrates, to yield the amides trans-( IR, 2/ )-3-phenylcyclopropane carbonitrile (49% conv. 22.7% ee), trans-( IS, 35)-2,2-dimethyl-3-phenylcyclopropanecarbonitrile (40% conv. 84.7% ee), trans-( IR, 3/f)-2,2-dibromo-3-phenylcy-clopropanecarbonitrile (11.6% conv. 83.8% ee), cis-( IR, 25)-3-phenylcyclopropanecarbonitrile (25.8% conv. 95.4% ee), and cis-(lR, 2S )-2,2-dimethyl-3-phenylcyclopropanecarbonitrile (7.9% conv. 3.2% ee) [43],... 

A careful study of the stereomutation of 2-phenylcyclopropane-l,3-d2-l-carbonitrile by Baldwin and Carter revealed that the reaction could be identified with exclusive cleavage of the bond between the two substituents. Thus the absolute configuration of the CHD carbon (C(3)) did not change, as indicated in Figure 16. 

U V irradiation of readily available oxirane-2-carbonitriles with at least one aromatic substituent attached to the three-membered ring results in a facile photofragmentation to cyanocarbenes and carbonyl compounds (see Houben-Weyl, Vol. E19b, pll98). In the presence of alkenes, cyclopropane-l-carbonitriles are formed (Table 1). This method is especially useful for the synthesis of 1-phenylcyclopropane-l-carbonitriles in moderate to good yields. ... 

The photofragmentation of easily accessible 2,2,2-triethoxy-4,5-diphenyl-l,3,2-dioxaphos-pholane-4,5-dicarbonitrile (1) results in the formation of cyano(phenyl)carbene. Reaction of the latter with alkenes leads to 1-phenylcyclopropane-l-carbonitriles 2 in high yield/ ... 

An experimental procedure for 2,2,3,3-tetramethyl-l -phenylcyclopropane-1 -carbonitrile can be found in Houben-Weyl, Vol. E19b, p 1207. 

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