Isomerisation of Primary Propargyl Alcohols to Vinyl Ketones Mediated by Hg(OAc)₂

Flow-Assisted Switchable Catalysis of Metal Ions in a Microenvelope System Embedded with Core–Shell Polymers

“…A further decrease in the flow rate did not lead to higher yield. In comparison, the conventional batch process required a long reaction time (12–24 h) and a stoichiometric amount of Hg 2+ catalyst under strongly acidic conditions to attain 65–90% conversion of alkynes. − It is well-documented that the intrinsic advantages of the microreactor such as high surface to volume ratio, and fast heat and mass transfer lead to accelerated reaction kinetics even in the presence of minimal catalyst loading. − …”

Preparation of the tricyclic ketopyrrole core of roseophilin by radical macrocyclisation and Paal–Knorr condensation

“…After desilylation, Yadav's procedure for isomerising propargylic 1Њ-alcohols to vinyl ketones 15 was assessed in the case of alcohol 14. The reported conditions [Hg(OAc) 2 , aq.…”

Formal synthesis of roseophilin

“…Generation of the lithium enolate from the intermediate silyl enol ether, trapping with propargylic iodide (propargyl = prop-2-ynyl) 11 9 and desilylation with fluorosilicic acid 10 afforded 1°-alcohol 2. Yadav's procedure for converting 1°-propargyl alcohols into vinyl ketones 11 was unsuccessful when applied to this substrate as the hydrogen sulfide used in the work-up led to thiol adducts that could not be processed further. Eventually we found that treatment of alcohol 2 with Hg(OAc) 2 in acetic acid containing water (1.0 equiv.)…”