Nitrile oxides alkene chiral centeres

In all of the above reactions, a chiral center of the alkene was located in the allylic position. However, as shall be demonstrated next, more distant chiral centers may also lead to highly selective cycloadditions with 1,3-dipoles. In two recent papers, the use of exocyclic alkenes has been applied in reactions with C,N-diphenylnitrone (165,166). The optically active alkenes 109 obtained from (S)-methyl cysteine have been applied in reactions with nitrones, nitrile oxides, and azomethine ylides. The 1,3-dipolar cycloaddition of 109 (R=Ph) with C,N-diphenyl nitrone proceeded to give endOa-1 Q and exOa-110 in a ratio of 70 30 (Scheme 12.36). Both product isomers arose from attack of the nitrone 68 at the... 

The use of alkenyl nitrile oxides is an effective method for the construction of bland polycyclic isoxazolines (2,4,200,236,237). Due to the rigid linear structure of the nitrile oxide, the reaction of alkenyl nitrile oxides almost always proceeds to give bicyclo[X,3,0] derivatives for X = 3-5. Most frequently, the diastereoselec-tivities are controlled by a chiral center on the link between the alkene and the dipole groups. 

An allylic chiral center between the nitrile oxide and alkene groups can also affect the stereochemistry of INOC reactions. For example, the production of only the cycloadduct (191) in the reaction of the (Z)-nitroalkene (190) (Scheme 90), compared to the formation of a 3 1 mixture of the isoxazolines (193) and (194) from the ( )-isomer (192) (Scheme 91) (84ACR410) is a dramatic example of the influence of allylic 1,3-strain (89CRV1841) on these processes. 

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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