10.1021/jo005692o
The research focuses on the stereoselective synthesis of hydroxylated R,γ-unsaturated nitriles, which are valuable synthetic intermediates that can be transformed into various carbocycles and heterocycles. The study aimed to develop an efficient method for synthesizing these compounds from readily available precursors, expanding on a key chelation-controlled conjugate addition-alkylation reaction. The researchers utilized a strategy involving sequential epoxidation and base-induced ring opening, optimizing the synthesis to prevent isomerization and polymerization of the highly water-soluble nitrile 1a. Key chemicals used in the process included m-CPBA for epoxidation, tosylates for conversion to nitriles, and lithium amide bases like LDA for the ring-opening reaction. The study concluded that hydroxy R,γ-unsaturated nitriles could be efficiently synthesized through the chelation-controlled ring opening of epoxy, tetrahydrofuranyl, and tetrahydropyranyl acetonitriles, providing a highly stereoselective two-step synthesis of trans-R,γ-unsaturated nitriles with hydroxylation on carbons successively removed from the double bond.
10.1021/acs.organomet.6b00650
The research investigates the comparative reactivity of three bisphosphine nickel(II) precatalysts—namely (L1)Ni(o-tol)Cl (C1), (L2)Ni(o-tol)Cl (C2), and (L3)Ni(o-tol)Cl (C3)—in nickel-catalyzed C(sp2)?N cross-coupling reactions. The study aims to evaluate how ancillary ligands influence catalytic performance in these transformations, which are essential for synthesizing biologically active molecules and functional materials. The chemicals used include ammonia, primary alkylamines such as furfurylamine and sec-butylamine, secondary dialkylamines like morpholine, and a range of aryl electrophiles including chlorides, bromides, and tosylates. The newly synthesized air-stable precatalyst C1, featuring an electron-rich JosiPhos CyPF-Cy ligand, was found to be competitive with and sometimes complementary to C2, especially in challenging room-temperature monoarylations of ammonia and primary alkylamines with (hetero)aryl chlorides.
10.1007/bf00806859
The research focuses on the synthesis of protected 2',3'-dideoxy-2'-hydroxymethyl nucleosides. These nucleosides, obtained through a multi-step procedure starting from isopropylideneglycerol, can be used as building blocks for the synthesis of 2',5'-ether linked oligonucleotides. The study aims to develop modified nucleosides that can be utilized in the creation of "Antisense" oligonucleotides, which have the potential to regulate gene expression and serve as therapeutic agents for viral and cancer treatments. Key chemicals involved in the research include isopropylideneglycerol (Solketal), tosylate, cyanessigester, and various protecting groups such as MBE (monomethoxytrityl) and DPTBSi (tert-butyldiphenylsilyl). The synthesis involves multiple steps, including alkylation, cyclization, reduction, and protection, with detailed characterization of the synthesized compounds using techniques like NMR spectroscopy. The research highlights the importance of these modified nucleosides in enhancing the stability and efficacy of oligonucleotides for potential pharmaceutical applications.
