Disulphide bond exchange inhibited by air – kinetic and thermodynamic products in a library of macrocyclic cysteine derivatives. Issue 14 (14th February 2018)

• Record Type: Journal Article
• Authors: Cholewiak, Agnieszka; Dobrzycki, Łukasz; Jurczak, Janusz; Ulatowski, Filip
• Is Part Of: Organic & biomolecular chemistry. Volume 16:Issue 14(2018)
• Page Start: 2411
• Page End: 2420
• Publication Date: 2018-02-14
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c7ob03123h
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Oxidation of dithiols provides strained monomeric macrocycles which transform upon disulphide bond exchange into stable dimers. Abstract : In this paper we present the synthesis and reactivity of dithiols comprising of two cysteine moieties attached to a dipicolinic acid core. Oxidation of these thiols provides oligomeric macrocycles. Monomers with 13-membered rings are kinetic products which are, however, strained and readily transform into higher oligomers under basic conditions or elevated temperature via a disulphide exchange reaction. Dimers, which are the most stable thermodynamic products, equilibrate only under inert conditions with thiolate as a catalyst. Under aerobic conditions, the thiols are oxidised before the equilibrium is reached.