371-41-5Relevant articles and documents
Unexpected phenol production from arylboronic acids under palladium-free conditions; Organocatalyzed air oxidation
Cammidge, Andrew N.,Goddard, Victoria H. M.,Schubert, Christopher P. J.,Gopee, Hemant,Hughes, David L.,Gonzalez-Lucas, Daniel
, p. 6034 - 6037 (2011)
An intriguing class of quinones that efficiently catalyze the air oxidation (overall hydroxylation) of arylboronic acids to the corresponding phenol is reported. Autocatalysis in the parent system is particularly efficient and leads to rapid, quantitative synthesis of quinones such as 4 from boronic acid 1 at room temperature using air as stoichiometric oxidant. The efficiency results from a balance between two-stage conjugate addition and migration with each step driven by aromatization of a naphthalene fragment.
Decarboxylative Hydroxylation of Benzoic Acids
Ritter, Tobias,Su, Wanqi,Xu, Peng
supporting information, p. 24012 - 24017 (2021/10/06)
Herein, we report the first decarboxylative hydroxylation to synthesize phenols from benzoic acids at 35 °C via photoinduced ligand-to-metal charge transfer (LMCT)-enabled radical decarboxylative carbometalation. The aromatic decarboxylative hydroxylation is synthetically promising due to its mild conditions, broad substrate scope, and late-stage applications.
Alkylsulfenyl thiocarbonates: precursors to hydropersulfides potently attenuate oxidative stress
Aggarwal, Sahil C.,Khodade, Vinayak S.,Paolocci, Nazareno,Pharoah, Blaze M.,Toscano, John P.
, p. 8252 - 8259 (2021/06/22)
The recent discovery of the prevalence of hydropersulfides (RSSH) species in biological systems suggests their potential roles in cell regulatory processes. However, the reactive and transient nature of RSSH makes their study difficult, and dependent on the use of donor molecules. Herein, we report alkylsulfenyl thiocarbonates as a new class of RSSH precursors that efficiently release RSSH under physiologically relevant conditions. RSSH release kinetics from these precursors are tunable through electronic modification of the thiocarbonate carbonyl group's electrophilicity. In addition, these precursors also react with thiols to release RSSH with a minor amount of carbonyl sulfide (COS). Importantly, RSSH generation by these precursors protects against oxidative stress in H9c2 cardiac myoblasts. Furthermore, we demonstrate the ability of these precursors to increase intracellular RSSH levels.
Photocatalytic Reductive C-O Bond Cleavage of Alkyl Aryl Ethers by Using Carbazole Catalysts with Cesium Carbonate
Yabuta, Tatsushi,Hayashi, Masahiko,Matsubara, Ryosuke
, p. 2545 - 2555 (2021/02/01)
Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.
