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Borane-amines undergo exclusive monoacetoxylation to trifluoroacetoxyborane-amines (TFAB-amines), which serve as chemoselective reagents for direct reductive amination of aldehydes and ketones. TFABNEt has been established as mild and highly selective compared to widely-used NaBHCN and Na(AcO)BH, even at higher temperatures with challenging substrates. A mechanism involving polyaminoborane formed dehydroacetoxylation of TFABNH has been described.
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http://dx.doi.org/10.1039/d2cc04173a | DOI Listing |
Chem Pharm Bull (Tokyo)
September 2025
Peptide Research Center, Chubu University, 1200 Matsumoto-cho, Kasugai, Aichi 487-8501, Japan.
Conventional peptide synthesis involves multiple protection and deprotection steps, and typically relies on stoichiometric amounts of coupling reagents and additives. This makes the process cumbersome, and results in poor atom economy and hazardous waste generation. Therefore, direct peptide bond formation using unprotected amino acids is a promising alternative.
View Article and Find Full Text PDFOrganometallics
June 2025
Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48104, United States.
This article describes a detailed investigation of the palladium-catalyzed coupling of aryl (pseudo)halides (ArX) with MSCF to form aryl trifluoromethylthioethers (ArSCF). Mechanistic organometallic studies are used to interrogate two key elementary steps of the catalytic cycle: (1) transmetalation of Pd(Ar)(X) complexes with MSCF and (2) Ar-SCF bond-forming reductive elimination. These studies reveal that tetramethylammonium trifluoromethylthiolate, NMeSCF, exhibits a combination of fast kinetics and high chemoselectivity for transmetalation.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
Noncanonical amino acids play a critical role in enhancing drug efficacy, specificity, pharmacokinetics, and other key therapeutic properties. However, their incorporation into peptides or small molecules often presents significant synthetic challenges. Late-stage modification of natural residues, after the primary structural framework of a molecule is established, offers an efficient strategy for generating analogue libraries.
View Article and Find Full Text PDFR Soc Open Sci
August 2025
Department of Chemistry, Shiraz University, Shiraz, Iran.
A novel, durable heterogeneous magnesium-supported catalyst, IRMOF-3@Di(2-pyridyl) ketone@Mg(II) (Di(2-pyridyl) ketone: Di-2pyk), was effectively synthesized using a convenient approach and fully characterized utilizing chemo-physical analysis techniques such as powder X-ray diffraction analysis, attenuated total reflection infrared spectroscopy, field emission scanning electron microscopy with energy-dispersive spectroscopy, transmission electron microscopy, CHN analysis, inductively coupled plasma optical emission spectroscopy, thermogravimetric analysis and Brunauer-Emmett-Teller measurements. This metal-organic framework-based nanocatalyst displayed excellent catalytic behaviour in chemoselective hydrogenation of five biomass-based carbonyl compounds of furfural, cinnamaldehyde, levulinic acid, vanillin and citral in addition to a variety of aliphatic, aromatic, and α,β-unsaturated aldehydes and ketones at room temperature in water in the presence of sodium borohydride as a mild and safe hydrogen source reagent. The leaching and reusability experiments of this catalyst exhibited stability and reactivity after four runs.
View Article and Find Full Text PDFJ Org Chem
August 2025
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China.
Chemoselective cyclodehydration of α-arylhydrazonoamides via an electrophilic activation strategy has been described. A series of polysubstituted 4-aminocinnolines are chemoselectively synthesized in 67-90% yields from α-arylhydrazono-β-oxoamides in the presence of hexaphenyloxodiphosphonium triflate (Hendrickson reagent) and triflic anhydride (TfO) at room temperature, whereas several substituted quinolino [3,2-]cinnolines are obtained in 64-77% yields under reflux. The readily available starting materials, mild conditions, good yields and high chemoselectivity make this novel synthetic protocol much attractive and practical.
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