O-Benzylation, selective

N-acylation, selective 25, 255 suppl. 26 -, O-benzylation, selective 20,150 suppl. 26... 

Catalytic hydrogenolysis of an O-benzyl protective group is a mild, selective method introduced by Bergmann and Zervas to cleave a benzyl carbamate (> NCO—OCH2C6H5 > NH) prepared to protect an amino group during pep-... 

On the other hand, addition of methylmagnesium bromide, as well as (triisopropoxy)methyl-titanium, to the O-benzyl-protected analog 4 proceeds with the facial stereoselection predicted by Cram s open-chain model, although the selectivities are very low72. 

The benzyl—nitrogen bond is not so easily cleaved as the benzyl—oxygen bond, unless the O-benzyl group is sterically hindered. This difference in activity allows the selective removal of the O-benzyl function in a molecule containing both N-benzyl and O-benzyl protecting groups. The selectivity can be reversed if the amine is protected by the Cbz group. If a small amount of amine (e g., butylamine) is added, then the selective removal of N-benzyl amines can be achieved.292... 

Two other myo-inositol derivatives have been selectively alkylated. Reaction of DL-l,2 4,5-di-0-cyclohexylidene-myo-inositol with benzyl chloride-potassium hydroxide in benzene, followed by removal of the acetal groups, gave DL-1-O- and DL-4-O-benzyl-myu-inositol in the ratio of 5 2, whereas, under similar conditions, DL-1,2 5,6-O-cyclohexylidene-myo-inositol gave311 the same ethers in the ratio of 57 10. These results are not readily explicable in the absence of knowledge of the conformations adopted by the cyclic acetals. 

Useful syntheses of D- and L-lyxose from 1,3-O-benzylidene-D- and L-arabinitol have been achieved through the highly selective oxidation of the primary hydroxyl groups by dimethyl sulfoxide-dicyclohexylcarbodiimide.463 Oxidation of but one of the two (equivalent) hydroxyl groups in 1,3,4,6-tetra-O-benzyl-D-mannitol464 and l,6-di-0-benzyl-2,5-0-methylene-D-mannitol465 was possible with dimethyl sulfoxide-acetic anhydride. 

Transformation of 2-deoxysugar derivatives into glycosyl xanthates can be performed by the treatment of O-benzyl-protected hemiacetal derivative with diphe-nylphosphoryl chloride, followed by the reaction with O-ethyl potassium xanthate in the presence of a base (NaOH, PTC reaction or NaH in appropriate organic solvent). High yields and selectivities in such reactions were observed when using sodium hydride in anhydrous THF [401],... 

O-stannylene acetals,84 glycals and 1,2-anhydrosugars,85 and to selective de-O-benzylation of position-2 with TIBAL, DIBAL-H57 or Lewis acid catalysts,86 or to the one-pot access to 3-O-benzyl-4,6-0-benzylidene glucosides by tandem catalysis recently reported.87 The 1,2-lactones recently reported by Linker and co-workers35 are also synthons which provide... 

The 3,4,5-tri-O-benzyl D-fructopyran derivative should lead to the spiro-pyran forms. Selective deprotection of the 4,5-O-isopropylidene, followed of perbenzylation and condensation with thiocyanic acid gave the expected spiro-pyran OZT in reasonable yield (53%), but standard acetylation was not very efficient for the separation of the two epimers (Scheme 26). 

Unprotected galactose derivatives may be readily transformed into the trichloroacetimidates 8a-8g, as shown in Table VIII. Again, as demonstrated for the O-benzyl-protected compounds 8a, either the a-trichloroace-timidate 8a-a or the / -trichloroacetimidate 8a -/ may be obtained highly selectively, depending on the base used for the catalysis of the addition to the trichloroacetonitrile. 

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