10.1016/j.tetlet.2012.03.030
The research primarily focuses on the development of complementary α-alkylation methods for the synthesis of sterically hindered spiro[pyrazolopyranpiperidine]ketone derivatives, which are potential treatments for type II diabetes. The experiments involve enolate alkylations using DMPU to enhance enolate reactivity and aldol condensations to access a diverse set of derivatives. Key reactants include ketone 2, LiHMDS, DMPU, various alkylating agents, aldehydes, and other reagents like SelectFluor? and Davis' oxaziridine. Analyses utilized include 1H and 13C NMR, IR spectroscopy, and mass spectrometry to characterize the synthesized compounds and confirm the success of the reactions. The study also explores the role of DMPU in enolate formation and reactivity through deuterium experiments, demonstrating its critical role in enhancing enolate reactivity and, in some cases, enolate formation.
10.1021/ja2041942
The research focuses on the development of a general method for the copper-catalyzed arylation of readily available 1H-perfluoroalkanes, a process of significant interest in the pharmaceutical and agrochemical industries due to the presence of aryl-trifluoromethyl or aryl-polyfluoroalkyl linkages in many drugs and agrochemicals. The method involves the use of aryl iodides and 1H-perfluoroalkanes as reactants, along with DMPU as a solvent, TMP2Zn as a base, and a copper chloride/phenanthroline catalyst system. The experiments aimed to optimize the reaction conditions with respect to ligand and solvent, and to explore the scope of the reaction with various aryl iodides and 1H-perfluoroalkanes. Analytical techniques such as 1H and 19F NMR, X-ray crystallography, and elemental analysis were employed to characterize the intermediates and products, while preliminary mechanistic studies were conducted to understand the reaction pathways, including the formation and reactivity of perfluoroalkyl copper species.
10.1021/ol900016g
The study presents an enantioselective synthesis method for C2-symmetric spirobilactams, which are important in synthetic chemistry due to their rigid spiro backbone that creates an effective asymmetric environment. The researchers used a Pd/BINAP complex as a catalyst to achieve an intramolecular double N-arylation of malonamides bearing 2-bromoarylmethyl groups, resulting in C2-symmetric spirobi(3,4-dihydro-2-quinolone) derivatives with up to 70% enantiomeric excess (ee). Key chemicals involved in the study include malonamides, bromoarenes, Pd(OAc)2 as the palladium source, (S)-BINAP as the chiral ligand, and various bases and solvents such as Cs2CO3, K3PO4, and DMPU. These chemicals served the purpose of facilitating the catalytic asymmetric synthesis, which is a highly practical method for preparing optically active spiranes, potentially useful as ligands and organocatalysts.
10.3390/molecules21111443
The study focuses on the characterization of the O-methyltransferase enzyme JerF, which is involved in the late stages of jerangolid biosynthesis. JerF is unique for its ability to catalyze the formation of a non-aromatic, cyclic methylenolether, a reaction not previously characterized in other O-methyltransferases. The researchers successfully overexpressed JerF in E. coli and utilized cell-free extracts to conduct bioconversion experiments. They also chemically synthesized a range of substrate surrogates to evaluate JerF's catalytic activity and substrate tolerance. The results revealed that JerF has a broad substrate tolerance and high regioselectivity, making it a promising candidate for chemoenzymatic synthesis, particularly for the modification of natural products containing a 4-methoxy-5,6-dihydro-2H-pyran-2-one moiety. The study also highlighted the potential of JerF in introducing specific methylation patterns and its use in biorthogonal coupling reactions, such as click chemistry, for site-specific labeling of biomolecules like DNA, RNA, or proteins.