4292-19-7Relevant articles and documents
Self-assembled ionophores as phase transfer catalysts
Marlow, Allison L.,Davis, Jeffery T.
, p. 3539 - 3542 (1999)
The nucleoside, 5'-(t-butyl-dimethylsilyl)-2',3'-O-isopropylidene isoG 1, catalyzes the S(N)2 reactions of alkali and ammonium iodides with dodecyl mesylate 2 under both liquid-liquid and solid-liquid phase transfer conditions. IsoG 1 self-associates to give a complex that extracts the salts into CDCl3 solution. Sodium iodide, in the presence of isoG 1, reacts faster with 2 than the other iodides under solid-liquid conditions. This reactivity difference is attributed to the open-faced structure of the ionophore-M+ complex under solid-liquid conditions.
Contra-thermodynamic Olefin Isomerization by Chain-Walking Hydroboration and Dehydroboration
Bloomer, Brandon,Butcher, Trevor W.,Ciccia, Nicodemo R.,Conk, Richard J.,Hanna, Steven,Hartwig, John F.
supporting information, p. 1005 - 1010 (2022/02/10)
We report a dehydroboration process that can be coupled with chain-walking hydroboration to create a one-pot, contra-thermodynamic, short-or long-range isomerization of internal olefins to terminal olefins. This dehydroboration occurs by a sequence comprising activation with a nucleophile, iodination, and base-promoted elimination. The isomerization proceeds at room temperature without the need for a fluoride base, and the substrate scope of this isomerization is expanded over those of previous isomerizations we have reported with silanes.
ω-Functionalized Lipid Prodrugs of HIV NtRTI Tenofovir with Enhanced Pharmacokinetic Properties
Bartsch, Perry W.,Basson, Adriaan E.,Burton, Samantha L.,Bushnev, Anatoliy,D'Erasmo, Michael,Dasari, Madhuri,Derdeyn, Cynthia A.,Giesler, Kyle E.,Hwang, Soyon S.,Iskandar, Sabrina,Liotta, Dennis C.,Miller, Eric J.,Pribut, Nicole,Raghuram, Akshay,Sharma, Savita K.
, p. 12917 - 12937 (2021/09/13)
Tenofovir (TFV) is the cornerstone nucleotide reverse transcriptase inhibitor (NtRTI) in many combination antiretroviral therapies prescribed to patients living with HIV/AIDS. Due to poor cell permeability and oral bioavailability, TFV is administered as one of two FDA-approved prodrugs, both of which metabolize prematurely in the liver and/or plasma. This premature prodrug processing depletes significant fractions of each oral dose and causes toxicity in kidney, bone, and liver with chronic administration. Although TFV exalidex (TXL), a phospholipid-derived prodrug of TFV, was designed to address this issue, clinical pharmacokinetic studies indicated substantial hepatic extraction, redirecting clinical development of TXL toward HBV. To circumvent this metabolic liability, we synthesized and evaluated ω-functionalized TXL analogues with dramatically improved hepatic stability. This effort led to the identification of compounds 21 and 23, which exhibited substantially longer t1/2 values than TXL in human liver microsomes, potent anti-HIV activity in vitro, and enhanced pharmacokinetic properties in vivo.
Photocatalytic Aerobic Phosphatation of Alkenes
Depken, Christian,Kr?tzschmar, Felix,Rieger, Rene,Rode, Katharina,Breder, Alexander
supporting information, p. 2459 - 2463 (2018/01/27)
A catalytic regime for the direct phosphatation of simple, non-polarized alkenes has been devised that is based on using ordinary, non-activated phosphoric acid diesters as the phosphate source and O2 as the terminal oxidant. The title method enables the direct and highly economic construction of a diverse range of allylic phosphate esters. From a conceptual viewpoint, the aerobic phosphatation is entirely complementary to traditional methods for phosphate ester formation, which predominantly rely on the use of prefunctionalized or preactivated reactants, such as alcohols and phosphoryl halides. The title transformation is enabled by the interplay of a photoredox and a selenium π-acid catalyst and involves a sequence of single-electron-transfer processes.
