Stereoselective Synthesis of α‐Trifluoromethyl Enones by Au^I/Cu^I‐Co‐Catalyzed Tandem 1,3‐Acyloxy Migration/Trifluoromethylation Reaction of Propargyl Acetates

Abstract

Dihydroxybenziphthalocyanine 1, with bulky aryloxy groups, has been synthesized and characterized by X‐ray crystallography, NMR and UV/Vis‐NIR spectroscopy, and theoretical calculations. Macrocycle 1 is the first example of an aromatic benziphthalocyanine with an 18π‐electron structure, and was found to exist as an equilibrium mixture of weakly aromatic and strongly aromatic tautomers. The aromaticity and near‐IR absorption can be controlled by chemical modification at the reactive resorcinol moiety and by variation of the solvent.

Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity

“… 308 α-Trifluoromethyl enones have been synthesized by a tandem 1,3-acyloxy migration/trifluoromethylation from 1-arylpropargyl esters with excellent stereoselectivity. 309 Propargylic 3-indoleacetates undergo a gold(I)-catalyzed tandem [3,3]-rearrangement/[2 + 2] cycloaddition to afford 2,3-indoline-fused cyclobutanes. 310 Other structures have also been accessed by reactions of propargyl carboxylates with gold(I), such as dihydrofurans, 311 aromatic ketones, 312 allenes, 313 or polyconjugated δ-diketones.…”

α‐Substituted Chalcones: A Key Review

“…AuI/CuI‐co‐catalyzed trifluoromethylation reaction of propargyl acetates was also applied to afford the desired α‐CF 3 enones including chalcones with excellent stereoselectivity (reaction 5, Figure 24). [97] Moreover, two α‐CF 3 ‐chalcones were synthesized using a silver(I) catalyzed regioselective trifluoromethylation of allenes and Langlois's salt (NaOSOCF 3 ) (reaction 6, Figure 24). [98] …”

Towards low-carbon energy state in South Africa: a survey of energy availability and sustainability

“…The Phase 1 successfully identified eight (8) REDZs, which yielded global minimum for environmental impact and global maximum for resource economic and social benefit on the South African map. The Phase 2 project was aimed at identifying more REDZs and reviewing the four tiers sensitivity maps developed during the Phase 1 using recent datasets [27]. Several rounds of bids have been rolled out in the past few years and the development of farms rolled out in the Round 4 presently under construction and more rounds are still in progress.…”