Organoboron Reagent‐Controlled Selective (Deutero)Hydrodefluorination

Abstract

Deuterium-labeled) CF 2 H-and CFH 2 -moieties are of high interest in drug discovery. The high demand for the incorporation of these fluoroalkyl moieties into molecular structures has witnessed significant synthetic progress, particularly in the (deutero)hydrodefluorination of CF 3 -containing compounds. However, the controllable replacement of fluorine atoms while maintaining high chemoselectivity remains challenging. Herein, we describe the development of a selective (deutero)hydrodefluorination reaction via electrolysis. The reaction exhibits a remarkable chemoselectivity control, which is enabled by the addition of different organoboron sources. The procedure is operationally simple and scalable, and provides access in one step to high-value building blocks for application in medicinal chemistry. Furthermore, density functional theory (DFT) calculations have been carried out to investigate the reaction mechanism and to rationalize the chemoselectivity observed.

Switching Monomer‐to‐Excimer Fluorescence by Noncovalent Interaction Competition Strategy

“…Organic stimuli-responsive smart luminescence materials generally exhibit distinct luminescence switching under application of external stimuli, which have attracted considerable attention due to their extensive applications in display, sensor, data storage, and information security. [1][2][3][4][5] Unlike covalent luminescence materials that rely on chemical synthesis, noncovalent of intermolecular interactions as an underlying driving force to construct the phase-transition system with explicit structural information. Specifically, the target molecule is designed to consist of two functional groups, benzo[d]thiazole (BZT) and pyrene (Py), corresponding to the formation of H-bonds and π-π interactions, respectively.…”

Electrochemically enabled C(sp3)–C(sp) cross-coupling of alkyl iodides, N-hydroxyphthalimide esters, and Katritzky salts with acetylenic sulfones

“…To date, there are very few examples of the electrochemical synthesis of internal alkynes. As part of our ongoing interest in developing electrochemical reactions via cathodic reduction, 26 we herein report a simple and efficient approach, using alkyl iodides and simple prefunctional compounds such as N -hydroxyphthalimide esters and Katritzky salts with acetylenic sulfones, through C(sp 3 )–C(sp) coupling reactions to synthesize various internal alkynes in decent yields (Scheme 1d).…”

Assignment of the absolute configuration of molecules that are chiral by virtue of deuterium substitution using chiral tag molecular rotational resonance spectroscopy

“…9 Recently, precision deuteration of small molecules has emerged at the forefront of new reaction discovery. [10][11][12][13][14][15][16][17][18][19][20][21][22] Precision deuteration techniques are used to control the exact placement and quantity of deuterium being installed into an organic molecule. This is challenging from both a synthetic and analytical perspective.…”

“…This has led to a high demand for efficient and selective deuterium incorporation reactions 9 . Recently, precision deuteration of small molecules has emerged at the forefront of new reaction discovery 10–22 . Precision deuteration techniques are used to control the exact placement and quantity of deuterium being installed into an organic molecule.…”