16404-66-3

Upstream product

• 527-60-6 Mesitol 
• 88-05-1 2,4,6-trimethylaniline 
• 527-61-7 2,6-dimethyl-1,4-benzoquinone 
• 917-54-4 methyllithium 
• 527-17-3 Duroquinone 
• 75-16-1 methylmagnesium bromide 
• 67-56-1 methanol 
• 78-83-1 2-methyl-propan-1-ol 
• 71-41-0 pentan-1-ol 
• 107-18-6 allyl alcohol 
• 75-65-0 tert-butyl alcohol 
• 75-75-2 methanesulfonic acid 
• 4380-68-1 2,4,6-trimethylbenzamide 
• 108-67-8 1,3,5-trimethyl-benzene 

Downstream Products

• 70328-76-6 1-acetoxy-2,3,4,6-tetramethylbenzene 
• 49583-05-3 3-acetoxy-2,4,6,trimethylphenyl acetate 
• 700-13-0 Trimethylhydroquinone 
• 1349842-30-3 tert-butyl (1,3,5-trimethyl-4-oxocyclohexa-2,5-dien-1-yl) malonate 
• 1217509-73-3 1,3,5-trimethyl-4-oxocyclohexa-2,5-dienyl 6-O-acetyl-2-deoxy-2-iodo-3,4-O-(1-methylethylidene)-β-D-galactopyranoside 
• 2233-18-3 4-hydroxy-3,5-dimethylbenzaldehyde 
• 527-61-7 2,6-dimethyl-1,4-benzoquinone 
• 33919-00-5 4-hydroperoxy-2,4,6-trimethyl-2,5-cyclohexadien-1-one 
• 527-60-6 Mesitol 
• 854726-50-4 4-hydroxy-2,4,6-trimethyl-5-phenyl-cyclohex-2-enone 
• 99647-82-2 2,4,6-trimethyl-3-hydroxybiphenyl 

Relevant academic research and scientific papers

Singlet oxygen generation from H2O2/MoO42-: Peroxidation of hydrophobic substrates in pure organic solvents

Seventeen organic solvents are screened as reaction media to conduct the molybdate-catalyzed disproportionation of hydrogen peroxide into singlet molecular oxygen, 1O2 (1Δg). The solvents are investigated by resorting to the detection of the infra-red luminescence of 1O2 at 1270 nm. Preparative peroxidations of representative substrates are carried out in the most efficient ones. The latter are protic and polar and constitute a simpler alternative to the well suited but more intricate microemulsion systems for the peroxidation of hydrophobic substrates with chemically generated 1O2.

Practical oxidative dearomatization of phenols with sodium hypochlorite pentahydrate

A highly efficient and practical oxidative dearomatization of phenols using sodium hypochlorite pentahydrate as an inexpensive, strong oxidant is reported for the first time. The oxidation reactions proceeded very rapidly in the presence of water to give the desired products in excellent yields, and sodium chloride and water were the only by-products derived from the oxidant.

PhSeBr mediated hydroxylative oxidative dearomatization of naphthols-an open air facile one-pot synthesis of ketols

A new methodology for oxidative-dearomatization of planar phenols is described. An economic, viable one-pot metal free protocol for direct conversion of naphthols to α-ketols is reported. Naphthols were found to undergo facile unprecedented oxidative dearomatization with regioselective hydroxylation with phenyl selenyl bromide in open air conditions. Quaternary stereocenters were developed along with formation of sterically demanding α- and γ-ketols with high yields. Functional group tolerance like esters is revealed. A thorough study of the stereoelectronic demands of the unusual oxy-selenium reactive intermediate involved in dearomatization of 1- and 2-naphthols is carried out. 4-Hydroxy cyclohexadieneone and cyclohexadieneone aryl ethers were generated from dialkyl-phenols under similar reaction conditions providing direct evidence of the mechanical postulate. The first instance of the phenoxy-selenium interaction leading to facile dearomatization of arenes is highlighted in this manuscript.

Tandem dienone photorearrangement-cycloaddition for the rapid generation of molecular complexity

A tandem dienone photorearrangement-cycloaddition (DPC) reaction of novel cyclohexadienone substrates tethered with various 2π and 4π reaction partners resulted in the formation of polycyclic, bridged frameworks. In particular, use of alkynyl ether-tether

Organophotocatalytic Aerobic Oxygenation of Phenols in a Visible-Light Continuous-Flow Photoreactor

A mild photocatalytic phenol oxygenation enabled by a continuous-flow photoreactor using visible light and pressurized air is described herein. Products for wide-ranging applications, including the synthesis of vitamins, were obtained in high yields by precisely controlling principal process parameters. The reactor design permits low organophotocatalyst loadings to generate singlet oxygen. It is anticipated that the efficient aerobic phenol oxygenation to benzoquinones and p-quinols contributes to sustainable synthesis.

Singlet Oxygen Generation from a Water-Soluble Hypervalent Iodine(V) Reagent AIBX and H2O2: An Access to Artemisinin

Herein, we report an efficient method for the chemical generation of 1O2 by treatment of H2O2 with AIBX, a highly water-soluble, bench-stable, recyclable hypervalent iodine(V) reagent developed by our group. The generation of 1O2 was confirmed by the following results: (1) capture of 1O2 with the sodium salt of anthracene-9,10-bis(ethanesulfonate) produced the corresponding endoperoxide and (2) TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) produced by the oxidation of 2,2,6,6-tetramethylpiperidine with 1O2 generated using the AIBX/H2O2 system was detected by electron spin resonance spectroscopy. To illustrate the potential utility of this method for organic synthesis, we used the AIBX/H2O2 system to perform typical reactions of 1O2: [2 + 2]/[4 + 2] cycloadditions, Schenck ene reactions, and heteroatom oxidation reactions, which afforded the corresponding products in high yields. Moreover, we used the method to synthesize the antimalarial drug artemisinin. Finally, we demonstrated that AIBX could be regenerated after the reaction by means of a workup involving extraction and removal of water to obtain a precursor of AIBX, which could then be re-oxidized.

Reductive Aromatization of Quinols with B2pin2 as Deoxidizing Agent

We have demonstrated B2pin2 as superior deoxidizing agent for the reductive deoxygenation of quinol derivatives under basic conditions. A wide range of highly functionalized phenols were obtained in good yields including a complex drug molecule, which revealed the high functional group tolerance of this protocol.

“Dark” Singlet Oxygen Made Easy

An operationally simple continuous flow generator of “dark” singlet oxygen has been developed. The singlet oxygen was efficiently reacted with several chemical traps to give the corresponding oxygenated products in high yields. The developed “dark” singlet oxygen generator has been successfully applied in the synthesis of the antimalarial drug artemisinin.

Site-selective Oxidative Dearomatization of Phenols and Naphthols into ortho-Quinols or Epoxy ortho-Quinols using Oxone as the Source of Dimethyldioxirane

A novel reactivity of dimethyldioxirane, generated in situ from Oxone and acetone, with substituted phenols and naphthols is reported. This methodology allowed the synthesis of ortho-quinols or epoxy ortho-quinols from a site-selective oxidative dearomatization process, with good yields under very mild conditions. A short total synthesis of natural product lacinilene C methyl ether is also described using this process as the key step. (Figure presented.).

An Enzymatic Route to α-Tocopherol Synthons: Aromatic Hydroxylation of Pseudocumene and Mesitylene with P450 BM3

Aromatic hydroxylation of pseudocumene (1 a) and mesitylene (1 b) with P450 BM3 yields key phenolic building blocks for α-tocopherol synthesis. The P450 BM3 wild-type (WT) catalyzed selective aromatic hydroxylation of 1 b (94 %), whereas 1 a was hydroxylated to a large extent on benzylic positions (46–64 %). Site-saturation mutagenesis generated a new P450 BM3 mutant, herein named “variant M3” (R47S, Y51W, A330F, I401M), with significantly increased coupling efficiency (3- to 8-fold) and activity (75- to 230-fold) for the conversion of 1 a and 1 b. Additional π–π interactions introduced by mutation A330F improved not only productivity and coupling efficiency, but also selectivity toward aromatic hydroxylation of 1 a (61 to 75 %). Under continuous nicotinamide adenine dinucleotide phosphate recycling, the novel P450 BM3 variant M3 was able to produce the key tocopherol precursor trimethylhydroquinone (3 a; 35 % selectivity; 0.18 mg mL?1) directly from 1 a. In the case of 1 b, overoxidation leads to dearomatization and the formation of a valuable p-quinol synthon that can directly serve as an educt for the synthesis of 3 a. Detailed product pattern analysis, substrate docking, and mechanistic considerations support the hypothesis that 1 a binds in an inverted orientation in the active site of P450 BM3 WT, relative to P450 BM3 variant M3, to allow this change in chemoselectivity. This study provides an enzymatic route to key phenolic synthons for α-tocopherols and the first catalytic and mechanistic insights into direct aromatic hydroxylation and dearomatization of trimethylbenzenes with O2.