Chorev M, Goodman M
Int J Pept Protein Res. 1983 Mar;21(3):258-68.
Several synthetic routes are reported to prepare the hetero diprotected 1,1-diaminoalkanes from N-acylated amino acids or peptides for incorporation into partially modified retro-inverso peptides. The Curtius rearrangement was carried out on the N-protected aminoacyl azides obtained from the N-protected aminoacyl hydrazide by nitrosyl chloride or by sodium azide reaction with an appropriate mixed carboxylic carbonic acid anhydride. The resulting isocyanate was allowed to react with alcohol to give a urethane-type protecting group or, via a "one-pot" approach, directly with a carboxyl carrying component to yield the modified (reversed) peptide bond. The carboxyl component can be either an N-acylated amino acid or a malonic acid. The more standard route involves selective deprotection of the 1,1-diaminoalkane residue followed immediately by coupling with a carboxyl component to yield the same modified peptide derivative.
据报道，有几种合成路线可从N-酰化氨基酸或肽制备杂二保护的1,1-二氨基烷烃，用于掺入部分修饰的反向肽中。通过亚硝酰氯或叠氮化钠与适当的混合羧酸碳酸酐反应，对由N-保护的氨基酰肼得到的N-保护的氨基酰叠氮化物进行库尔提斯重排。使生成的异氰酸酯与醇反应得到氨基甲酸酯型保护基，或者通过“一锅法”直接与带有羧基的组分反应，生成修饰的（反向的）肽键。羧基组分可以是N-酰化氨基酸或丙二酸。更标准的路线是先对1,1-二氨基烷烃残基进行选择性脱保护，然后立即与羧基组分偶联，得到相同的修饰肽衍生物。
