Gold-Catalyzed Alkynylative Meyer-Schuster Rearrangement.

Area of Science:

• Organic Chemistry
• Catalysis
• Synthetic Methodology

Background:

• The Meyer-Schuster rearrangement is a crucial transformation for synthesizing carbonyl compounds.
• Gold catalysis offers unique reactivity for various organic transformations.
• Developing novel catalytic cycles is essential for advancing synthetic chemistry.

Purpose of the Study:

• To design and implement the first alkynylative Meyer-Schuster rearrangement.
• To utilize gold catalysis in a novel
• interplay
• mode combining π-activation and cross-coupling.
• To provide a straightforward synthesis of enynones from propargyl alcohols.

Main Methods:

• Application of gold catalysis in an "interplay" mode.
• Utilizing propargyl alcohol as a feedstock.
• Employing control experiments to identify the active catalyst.
• Reaction monitoring using Electrospray Ionization High-Resolution Mass Spectrometry (ESI-HRMS).

Main Results:

• Successful implementation of the first alkynylative Meyer-Schuster rearrangement.
• Straightforward access to enynones, valuable synthetic intermediates.
• Evidence supporting an Au(III) catalyst initiating the rearrangement.
• Identification of a key alkynylgold(III) intermediate, validating the "interplay" mechanism.

Conclusions:

• The developed protocol offers an efficient route to enynones.
• The proposed "interplay" mode of gold catalysis is supported by experimental evidence.
• This work expands the scope of gold-catalyzed reactions and Meyer-Schuster rearrangements.