1609537-97-4

Upstream product

• 98-54-4 para-tert-butylphenol 

Downstream Products

• 4857-70-9 2-tert-butyl-5-hydroxy-1,4-benzoquinone 
• 36122-03-9 4-tert-butyl-5-methoxy-1,2-benzoquinone 
• 1774-86-3 5-tert-butyl-2-methoxy-1,4- benzoquinone 
• 662126-11-6 4-tert-butyl-5-ethoxy-1,2-benzoquinone 
• 1774-87-4 2-Aethoxy-5-tert-butyl-p-benzochinin 

Relevant academic research and scientific papers

A Bioinspired Catalytic Aerobic Functionalization of Phenols: Regioselective Construction of Aromatic C-N and C-O Bonds

We report a bioinspired approach for the regioselective construction of both aromatic C-O and C-N bonds through the dehydrogenative coupling of phenols and aliphatic amines. Mechanistically, the process hinges on the ortho-oxygenation of phenols to ortho-quinones followed by aromatic C-N bond formation through a condensation/redox isomerization cascade. Overall, the process enables the regioselective formation of aromatic C-O and C-N bonds directly from C-H bonds under mild reaction conditions.

A Biomimetic Mechanism for the Copper-Catalyzed Aerobic Oxygenation of 4-tert-Butylphenol

Controlling product selectivity during the catalytic aerobic oxidation of phenols remains a significant challenge that hinders reaction development. This work provides a mechanistic picture of a Cu-catalyzed, aerobic functionalization of phenols that is selective for phenoxy-coupled ortho-quinones. We show that the immediate product of the reaction is a Cu(II)-semiquinone radical complex and reveal that ortho-oxygenation precedes oxidative coupling. This complex is the resting state of the Cu catalyst during turnover at room temperature. A mechanistic study of the formation of this complex at low temperatures demonstrates that the oxygenation pathway mimics the dinuclear Cu enzyme tyrosinase by involving a dinuclear side-on peroxodicopper(II) oxidant. Unlike the enzyme, however, the rate-limiting step of the ortho-oxygenation reaction is the self-assembly of the oxidant from Cu(I) and O2. We provide details for all steps in the cycle and demonstrate that turnover is contingent upon proton-transfer events that are mediated by a slight excess of ligand. Finally, our knowledge of the reaction mechanism can be leveraged to diversify the reaction outcome. Thus, uncoupled ortho-quinones are favored in polar, coordinating media, highlighting unusually high levels of chemoselectivity for a catalytic aerobic oxidation of a phenol. (Chemical Equation Presented).

A divergent and selective synthesis of ortho- and para-quinones from phenols

Abstract We describe a divergent synthesis of substituted ortho- and para-quinones by catalytic aerobic oxygenation of phenols. Substituted quinones are omnipresent in chemistry and biology, but their synthesis frequently suffers from low efficiency and poor scope. Our methodology employs a catalytic aerobic di-functionalization of phenols to aryloxy-ortho-quinones. Regioselective substitution with an alcohol provides the alkoxy substituted ortho- or para-quinone, while hydrolysis affords the para-hydroxyquinone. These are mild and selective conditions for the synthesis of diversely substituted quinones from readily available phenol starting materials.

Catalytic aerobic oxidation of phenols to ortho-quinones with air-stable copper precatalysts

A range of air-stable copper species was examined for catalytic activity in the catalytic aerobic transformation of phenols into ortho-quinones. Efficient catalysis was obtained with commercially available copper(ii) acetate. The stability of all constitu

A biomimetic catalytic aerobic functionalization of phenols

The importance of aromatic C-O, C-N, and C-S bonds necessitates increasingly efficient strategies for their formation. Herein, we report a biomimetic approach that converts phenolic C-H bonds into C-O, C-N, and C-S bonds at the sole expense of reducing dioxygen (O2) to water (H 2O). Our method hinges on a regio- and chemoselective copper-catalyzed aerobic oxygenation to provide ortho-quinones. ortho-Quinones are versatile intermediates, whose direct catalytic aerobic synthesis from phenols enables a mild and efficient means of synthesizing polyfunctional aromatic rings. The direct approach: Polyfunctional aromatic rings have been generated by direct functionalization of C-H bonds to C-O, C-N, and C-S bonds at the sole expense of reducing O2 to H2O. The method hinges on a regio- and chemoselective, copper-catalyzed aerobic oxygenation of phenols to provide ortho-quinones (see scheme), thus mimicking the ubiquitous biosynthetic pathway of melanogenesis.