Tertiary aryl squaramides were synthesized by using copper catalyzed C-N bond-formation with L-proline as the ligand. Symmetrical diaryl squaramides could be prepared in a one-pot reaction by using excess aryl bromide with varying yields. Unsymmetrical derivatives were prepared by sequential arylation. Yields of the diarylated products were highly sensitive to steric effects.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/jo070393l | DOI Listing |
Angew Chem Int Ed Engl
August 2024
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China.
β-Chiral carboxylic acids and their derivatives are highly valuable structural motifs in the fields of asymmetric synthesis and medicinal chemistry. However, the introduction of a sterically demanding sidechain to the β-carbon, such as an all-carbon quaternary center, remains a significant challenge in classical polar processes. Recently, N-heterocyclic carbene (NHC) mediated coupling reactions involving persistent ketyl radicals have emerged as a promising strategy to assemble highly crowded carbon-carbon bonds.
View Article and Find Full Text PDFJ Org Chem
June 2020
School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
High-level quantum chemical calculations were used to elucidate the gas- and solution-phase conformational equilibria for a series of symmetrically substituted (thio)ureas, (thio)squaramides, and croconamides. Gas-phase calculations predict that the thermodynamic conformer of many of these anion receptors is not the dual-hydrogen-bond-facilitating anti-anti conformer as is commonly assumed. For ,'-diaryl thiosquaramides and croconamides, the syn-syn conformer is typically the predominant conformer.
View Article and Find Full Text PDFChemistry
January 2018
School of Chemistry, The University of Sydney, NSW, 2006, Australia.
Dual H-bond donors are widely used as recognition motifs in anion receptors. We report the synthesis of a library of dual H-bond receptors, incorporating the deltic and croconic acid derivatives, termed deltamides and croconamides, respectively, and a comparison of their anion binding affinities (for monovalent species) and Brønsted acidities to those of the well-established urea and squaramide dual H-bond donor motifs. For dual H-bonding cores with identical substituents, the trend in Brønsted acidity is croconamides>squaramides>deltamides>ureas, with the croconamides found to be 10-15 pK units more acidic than the corresponding ureas.
View Article and Find Full Text PDFJ Org Chem
June 2010
Department of Chemistry, Lash Miller Laboratories, University of Toronto, 80 St George Street, Toronto ON M5S 3H6, Canada.
Zinc trifluoromethanesulfonate promotes efficient condensations of anilines with squarate esters, providing access to symmetrical and unsymmetrical squaramides in high yields from readily available starting materials. Efficient access to electron-deficient diaryl squaramides has enabled a systematic investigation of the colorimetric anion-sensing behavior of a p-nitro-substituted squaramide. Its behavior differs in dramatic and unexpected ways from that of structurally similar p-nitroaniline-based ureas, an effect that highlights the remarkable differences in acidity between the squaramide and urea functional groups.
View Article and Find Full Text PDFJ Org Chem
May 2007
Department of Chemistry and Biochemistry, Queens College and the Graduate Center of the City University of New York, Flushing, New York 11367-1597, USA.
Tertiary aryl squaramides were synthesized by using copper catalyzed C-N bond-formation with L-proline as the ligand. Symmetrical diaryl squaramides could be prepared in a one-pot reaction by using excess aryl bromide with varying yields. Unsymmetrical derivatives were prepared by sequential arylation.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!