Allyl group removal

For a modification of the allyl group removal procedure, see A. Merzouk and F. Guibe, Tetrahedron Lett., 1992, 33, 477. 

Three selective methods to remove protective groups are receiving much attention assisted, electrolytic, and photolytic removal. Four examples illustrate assisted removal of a protective group. A stable allyl group can be converted to a labile vinyl ether group (eq. 4) a /3-haloethoxy (eq. 5) or a /3-silylethoxy (eq. 6) derivative is cleaved by attack at the /3-substituent and a stable o-nitro-phenyl derivative can be reduced to the o-amino compound, which undergoes cleavage by nucleophilic displacement (eq. 7) ° ... 

The allyl group was used to protect the nitrogen in a /3-lactam synthesis, but was removed in a four-step sequence. Whether a transition-metal-catalyzed isomerization to the enamide followed by hydrolysis is an effective cleavage procedure remains to be tested and warrants further study. ... 

NBS, CH3CN, H2O, 62-90% yield. " The POM group has been selectively removed in the presence of an ethoxy ethyl ether, a TBDMS ether, a benzyl ether, a p-methoxybenzyl ether, an acetate, and an allyl group. Because the hydrolysis of a pentenyl 2-acetoxyglycoside was so much slower than a pentenyl 2-benzyloxyglycoside, the 2-benzyl derivative could be cleaved selectively in the presence of the 2-acetoxy derivative. The POM group is stable to 75% AcOH, but is cleaved by 5% HCl. 

The use of Pd(Ph3P)4 and MA -dimethylbarbituric acid removed the allyl group in 98% yield. 

The allyl group was used to protect the nitrogen in a j3-lactam synthesis, but was removed in a four-step sequence. ... 

Allyl carbamates also can serve as amino-protecting groups. The allyloxy group is removed by Pd-catalyzed reduction or nucleophilic substitution. These reactions involve formation of the carbamic acid by oxidative addition to the palladium. The allyl-palladium species is reductively cleaved by stannanes,221 phenylsilane,222 formic acid,223 and NaBH4,224 which convert the allyl group to propene. Reagents... 

Allyl groups attached directly to amine or amide nitrogen can be removed by isomerization and hydrolysis.228 These reactions are analogous to those used to cleave allylic ethers (see p. 266). Catalysts that have been found to be effective include Wilkinson s catalyst,229 other rhodium catalysts,230 and iron pentacarbonyl.45 Treatment of /V-allyl amines with Pd(PPh3)4 and (V,(V -dimethylbarbi Lurie acid also cleaves the allyl group.231... 

Products of this type were not isolated, however, when the non-immobilised metathesis substrates were allyl esters or ethers. In these cases, the combined effect of metathesis and TFA cleavage was simply to remove the allyl group. A modified protodesilylation mechanism was proposed to account for these results (Scheme 3). 

Pd(0)-catalyzed allylations of 4(5)-nitroimidazole, 2-methyl-4(5)-nitroimidazole, 4(5)-bromoimidazole and 4(5)-methoxyimidazole resulted in complicated mixtures, which did not necessarily reflect the tautomeric ratios of the starting material [7], For example, poor regioselectivity for the products (70 and 71) was observed in the Tsuji-Trost reaction of 4(5)-bromoimidazole with cinnamyl carbonate. However, the same reaction with 4(5)-nitroimidazole and 2-methyl-4(5)-nitroimidazole led predominantly to the l-allylation products. In addition, removal of the 77-imidazole allyl groups can be selectively effected under mild conditions by Pd-catalyzed ic-allyl chemistry [55],... 

It is interesting to note that this methodology allows the preparation of 4-functionalized indole derivatives starting from a simple acyclic precursor in a one-pot sequence. To prepare N-unsubstituted indoles, we choose the allyl moiety as a result to its stability to strong basic conditions and the variety of methods for its removal.[20] We therefore used an approach based on the isomerization/hydrolysis of the allyl groups with diisobutylaluminium hydride (DIBAL-H) and a... 

The dissociative mechanism can explain both facts in that the hydrogen removed in the first step may recombine with an isomeric form of the ally lie intermediate to yield the isomeric olefin. Apparently syn and anti 7T-allylic complexes [67, 68) retain their configurations unless each may be converted into a common a-bonded complex in which the nonterminal carbon atoms of the allyl group are connected by a single bond and the isomerization of the intermediate can be represented as in Fig. 11. However, the recombination of the hydrogen atom with the allylic intermediate must be faster than the rate at which it enters the surface pool of... 

Ru(H20)6], which is a precursor of ROM polymerization of cyclic dienes has also been found to possess good alkene isomerization activity [1], Among others it catalyzed the isomerization of allylphenyl ether to a vinylphenyl ether (Scheme 9.1) at room temperature. Allyl ethers are stable to acids and bases, while vinyl ethers are easily cleaved in acidic solutions. Therefore this isomerization gives a mild method for removal of protecting allyl groups under exceedingly mild conditions. 

Example 22 removal of allyl group attached to a phosphorus centre with Pd, Pt and Rh complexes is a well established procedure [51] but is inconvenient for synthesis of therapeutic compounds on a large scale. During the deprotection step the palladium catalyst is susceptible to poisoning especially with P-S compounds resulting in loss of catalytic efficiency. Furthermore traces of organometallic compounds remain in the product after deprotection. In the paper of Manoharan et al. other methods of deprotection of allyl... 

The allyl group, a less familiar protective group for carboxylic acids, can be easily removed from esters by treatment with sodium hydrogen telluride. In contrast to the preceding methods, ethanol has been employed as the solvent. 

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