Methods for the stereoselective synthesis of 2-fluoroalkenoates. Carbonyl condensation reactions of 3,3-bis(methylthio)-2-fluoropropenal, a highly-functionalized fluoroacrylate cation equivalent

Stereoselective Ring‐Opening of gem‐Difluorocyclopropanes: An Entry to Stereo‐defined (E,E)‐ and (E,Z)‐Conjugated Fluorodienes

“…However, the yields are generally modest and the products are typically obtained with moderate to good ( E , E )/( E , Z ) selectivity. Nonetheless, the olefination approach has found applications to prepare fluoro‐olefins, or fluorodienes such as fluoro‐retinal . In addition, fluorinated phosphonates could be used to construct mono‐ or difluorinated conjugated dienes .…”

O-Alkyl Hydroxamates as Metaphors of Enzyme-Bound Enolate Intermediates in Hydroxy Acid Dehydrogenases. Inhibitors of Isopropylmalate Dehydrogenase, Isocitrate Dehydrogenase, and Tartrate Dehydrogenase1

“…The data show that insertion of the “hydroxylamine” oxygen results in over a 1000-fold increase in affinity, with 2 showing nanomolar inhibitory potency. Furthermore, it is an uncompetitive inhibitor against isocitrate, in support of the idea that it mimics the enolate . That compound 2 binds to the form of the enzyme bearing reduced cofactor (NADH) was further shown by studying its inhibition of the reverse reaction with ketoglutarate as substrate (competitive, K i = 90 nM).…”

Development of a flow method for the hydroboration/oxidation of olefins

“…The combined stream was then combined at a T-piece with an aqueous solution of NaOH (0.42 M in H 2 O 2 (20% v/v)-H 2 O-EtOH 20 : 42 : 38) and reacted at rt in a 4.2 mL PFA reactor coil. To the resulting mixture, an aqueous saturated solution of NH 4 Cl was added, phases were separated and the organic layer extracted with Et 2 O (3×). Combined organic layers were washed with H 2 O (3×) and brine (1×), dried and evaporated.…”

“…The resulting mixture was stirred for 1 hour, warmed to room temperature and kept for an additional two hours at 80°C. The reaction was then allowed to cool before quenching by the addition of a saturated aqueous solution of NH 4 Cl. An aqueous layer was extracted with Et 2 O (3×).…”

“…The preparation of molecular entities containing the hydroxyl functionality is a very important area of research due to the abundance of this functional group in natural products and biologically active molecules. The toolbox of chemical reactions contain many examples of procedures that accomplish this transformation, such as direct oxidation of allylic C-H bonds by selenium, 1 C-H bond 2 oxidation by peracids, singlet oxygen oxidation, 3 treatment of diazo compounds with mineral acids, 4 silane oxidation by peracids, 5 ozonolysis of alkenes followed by reductive workup 6 or hydroboration-oxidation tandem reaction of alkenes. 7 Among them, the hydroboration-oxidation reaction has frequently been used for the insertion of hydroxyl groups either in total synthesis of natural products 8 or drug discovery.…”