Wiśniewski K, Kołdziejczyk A S, Falkiewicz B
Faculty of Chemistry, University of Gdańsk, Poland.
J Pept Sci. 1998 Feb;4(1):1-14. doi: 10.1002/(sici)1099-1387(199802)4:1<1::aid-psc132>3.0.co;2-r.
The Mitsunobu reaction--the nucleophilic substitution of an alcoholic hydroxyl group mediated by the redox system trialkylphosphine/dialkyl azodicarobxylate--is widely used in the chemistry of biologically active compounds. The paper deals with applications of the Mitsunobu reaction in amino acid and peptide chemistry. The process provides easy access to many unnatural amino acids and derivatives. Since the reaction occurs with complete inversion of the configuration at the carbinol chiral centre, it can be used for the synthesis of diastereoisomers of hydroxy- and tioprolines. Cyclization of beta-hydroxy amino acid containing peptides under Mitsunobu reaction conditions leads to a constrained peptide that mimics the stabilizing reverse turn secondary structure.
光延反应——由氧化还原体系三烷基膦/偶氮二甲酸二烷基酯介导的醇羟基的亲核取代反应——在生物活性化合物化学中被广泛应用。本文论述了光延反应在氨基酸和肽化学中的应用。该过程为许多非天然氨基酸及其衍生物的制备提供了便利途径。由于该反应在甲醇手性中心发生构型完全翻转，因此可用于合成羟基脯氨酸和硫代脯氨酸的非对映异构体。在光延反应条件下，含β-羟基氨基酸的肽环化生成一种模拟稳定反向转角二级结构的受限肽。
