A Robust and General Protocol for the Lewis‐Base‐Catalysed Reaction of Alcohols and Alkyl Propiolates. Issue 1 (31st October 2013)

• Record Type: Journal Article
• Authors: Tejedor, David; Álvarez‐Méndez, Sergio J.; López‐Soria, Juan M.; Martín, Víctor S.; García‐Tellado, Fernando
• Is Part Of: European journal of organic chemistry. Issue 1(2014)
• Page Start: 198
• Page End: 205
• Publication Date: 2013-10-31
• Subjects: Alkynes -- Organocatalysis -- ­Amines -- Alcohols -- Vinyl ethers; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201301303
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: A general and practical protocol for the tertiary‐amine‐catalysed synthesis of β‐alkoxyacrylates from primary, secondary, and tertiary alcohols is described. Of the currently used catalysts, DABCO proved to be the best one for this process. Three factors seem to influence the outcome of the reaction: (1) the nucleophilic strength of the catalyst, (2) the electrophilicity of the intermediate ammonium acrylate, and (3) the p K a /nucleophilicity of the alcohol/alkoxide nucleophile. Reactivity tuning enables the transformation of a range of tertiary alcohols into the corresponding β‐alkoxyacrylate derivatives. Differences in the reactivity of different types of alcohol allow the selective transformation of diols containing two different hydroxy groups into the corresponding monoprotected derivatives. This protocol will aid other synthetic organic chemists to easily prepare such vinyl ethers under atom‐economic, efficient, and bench‐friendly reaction conditions. Abstract : A practical protocol for the DABCO‐catalysed synthesis of β‐alkoxyacrylates is described. The protocol is efficient and economical, and it allows the transformation of a range of alcohols (including tertiary alcohols) into the corresponding β‐alkoxyacrylate derivatives and the selective monoprotection of different diols (primary vs. secondary and tertiary).