Protecting groups modifier

The following derivatives represent protective groups that contain an auxiliary functionality, which when chemically modified, results in intramolecular, assisted cleavage, thus increasing the rate of cleavage over simple basic hydrolysis. 

The final deprotection step must be modified to accommodate the new protective group (ANM) and an isolation method for a suitable crystalline form of 2 had to be developed. 

Taking Tomioka s pioneering work [8] as a precedent, we have screened 13-amino alcohols as chiral modifiers [9] in the nucleophilic addition of lithium 2-pyridinylacetylide 6 to the pMB protected ketimine 5. We were pleased to discover that when 5 was treated with a mixture prepared from 1.07 equiv each of quinine and 2-ethynylpyridine by addition of 2.13 equiv of n-BuLi in THF at -40 to -20 °C, the desired adduct 19 was obtained in 84% yield with maximum 64% ee. Soon after, we found selection of the nitrogen protective group had great influence on the outcome of the asymmetric addition and the ANM (9-anthranylmethyl)... 

It would be ideal if the asymmetric addition could be done without a protecting group for ketone 36 and if the required amount of acetylene 37 would be closer to 1 equiv. Uthium acetylide is too basic for using the non-protected ketone 36, we need to reduce the nucleophile s basicity to accommodate the acidity of aniline protons in 36. At the same time, we started to understand the mechanism of lithium acetylide addition. As we will discuss in detail later, formation of the cubic dimer of the 1 1 complex of lithium cyclopropylacetylide and lithium alkoxide of the chiral modifier3 was the reason for the high enantiomeric excess. However, due to the nature of the stable and rigid dimeric complex, 2 equiv of lithium acetylide and 2 equiv of the lithium salt of chiral modifier were required for the high enantiomeric excess. Therefore, our requirements for a suitable metal were to provide (i) suitable nucleophilicity (ii) weaker basicity, which would be... 

The suitability of the Aloe group for the construction of lipidated peptides is emphasized by the synthesis of the maleimidocaproyl-modified, S-palmi-toylated and farnesylated heptapeptide 16 which corresponds to the N-Ras C-terminus (Scheme 10).1211 In contrast to classical urethane-type protecting groups, the Aloe group can be removed in the presence of additional functional groups and under neutral conditions. It is therefore a very convenient protecting group for the synthesis of very hydro-phobic lipid-modified peptides, which are not soluble in the aqueous media required for enzyme catalyzed transformations. 

On the other hand, ligand 3b may be modified at the carboxylate donor instead of the OH-linker. This prevents the carboxylate donor from acting as linking group. Although the most obvious protecting group is the methyl ester 52 (Scheme 27), direct esterification of... 

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