title: Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.
abstract: Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product.
authors.affiliation: School of Engineering and Science, Chemistry, Jacobs University Bremen , 28759 Bremen, Germany.
authors.forename: Sagar
authors.initials: S
authors.lastname: Deshpande
authors.forename: Rakesh
authors.initials: R
authors.lastname: Jaiswal
authors.forename: Marius Febi
authors.initials: MF
authors.lastname: Matei
authors.forename: Nikolai
authors.initials: N
authors.lastname: Kuhnert
mesh_terms: D002726:Chlorogenic Acid / Q000737:chemistry; D040503:Coffea / Q000737:chemistry*; D004951:Esterification; D005511:Food Handling / Q000379:methods*; D006358:Hot Temperature; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007783:Lactones / Q000737:chemistry; D011801:Quinic Acid / Q000031:analogs & derivatives* / Q000737:chemistry; D012639:Seeds / Q000737:chemistry*; D014867:Water
chemical_list: D007783:Lactones; C472707:caffeoylquinic acid; D011801:Quinic Acid; D014867:Water; D002726:Chlorogenic Acid
keywords: acyl migration; brewing; chlorogenic acids; coffee; roasting; transesterification reaction