Bestmann ylide [(triphenylphosphoranylidene)ketene] acts as a chemical linchpin that links nucleophilic entities, such as alcohols or amines, with carbonyl moieties to produce unsaturated esters and amides, respectively. In this work, the formation of α,β,γ,δ-unsaturated esters (dienoates) is achieved through the coupling of Bestmann ylide, an alcohol and an α,β-unsaturated aldehyde. Primary an...

Abstract Polarized alkynes such as ynol ethers and ynamides have attracted much attention due to their inherent unique reactivity. Herein, we report Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions of aryl with allylic alcohols. At the first stage (hydroalkoxylation) this reaction, attack alcohols or occurs at ?-position polarized in a completely regioselective manner. ...

Sawadjoon, S. 2013. Palladium-Catalyzed Nucleophilic Substitution of Alcohols. Mechanistic Studies and Synthetic Applications. Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1092. 63 pp. Uppsala: Acta Universitatis Upsaliensis. ISBN 978-91-554-8785-0. This thesis deals with the palladium-catalyzed nucleophilic substitution of π-activated alco...

Gold(I)-chloride-catalyzed synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α-sulfenylated aldehydes and ketones in 60-97% yield. Secondary aliphatic propargylic alcohols generated α-sulfenylated ketones in...

A novel fast, convenient and inexpensive synthesis of 1',3'-dioxo-1',3'-dihydrospiro[cyclopropane-1,2'-indene]-2,2,3,3-tetracarbonitrile and dimethyl 2,3-dicyano-1',3'-dioxo-1',3'-dihydrospiro[cyclopropane-1,2'-indene]-2,3-dicarboxylate is reported. These compounds undergo double carbanion cleavage under the action of alcohols resulting in the formation of stable salts, containing new allylic-t...

We describe herein a palladium-catalyzed Heck-type reaction of O-acetyl ketoximes and allylic alcohols to synthesise pyridines. This protocol allows the robust synthesis of pyridines and azafluorenones in good to excellent yields with tolerance of various functional groups under mild conditions. The reaction is supposed to go through an oxidative addition of oximes to palladium(0) complexes, ge...

We have investigated the use of chiral silylating reagents as analytical probes for determining the absolute stereochemistry of natural products by NMR spectroscopy. These reagents are prepared in high chemical yield in one step and can be used to derivatize chiral allylic alcohols which are incompatible with ester-based methodologies. Microscale ( approximately 400 nmol) derivatization conditi...