19641-57-7

Upstream product

• 4111-08-4 2-hydroxy-2-methyl-butyronitrile 
• 18428-18-7 1-methyl-1-phenylpropyl hydroperoxide 
• 10467-10-4 ethylmagnesium iodide 
• 98-86-2 acetophenone 
• 925-90-6 ethylmagnesium bromide 
• 78-93-3 butanone 
• 2085-88-3 2-methyl-2-phenyloxirane 
• 75-16-1 methylmagnesium bromide 
• 80473-70-7 (lithium)2(CN)(methyl)2cuprate 
• 4564-81-2 1-phenyl-1,2-dimethyloxirane 
• 2039-93-2 1-ethylstyrene 
• 13144-95-1 2-chloro-2-phenylbutane 
• 33603-06-4 (+)-1-amino-2-phenylbutane 
• 52117-58-5 1-(p-tolylsulfinyl)-2-phenyl-2-butanol 

Downstream Products

• 4820-06-8 2-phenyl-2-methoxybutane 
• 1038-30-8 Mono(alpha-ethyl-alpha-methylbenzyl)phthalate 
• 18551-14-9 trimethyl-(1-methyl-1-phenyl-propoxy)-silane 
• 767-99-7 2-phenylbut-2-ene 
• 13144-95-1 2-chloro-2-phenylbutane 
• 143982-18-7 (1-bromo-1-methyl-propyl)-benzene 
• 101746-80-9 (1-methyl-1-phenyl-propyl)-p-tolyl sulfone 
• 18428-18-7 1-methyl-1-phenylpropyl hydroperoxide 
• 767-99-7 (Z)-2-phenylbut-2-ene 
• 768-00-3 (E)-2-phenyl-2-butene 
• 5011-60-9 4-nitro-benzoic acid-(1-methyl-1-phenyl-propyl ester) 
• 111583-92-7 1,3-diethyl-1-methyl-3-phenyl-indan 
• 52392-57-1 2-bromo-3-phenyl-but-2c-ene 
• 52392-58-2 2-bromo-3-phenyl-but-2t-ene 

Relevant academic research and scientific papers

On the effect of backbone modifications in 3,3-dimethyl-1-(trifluoromethyl)-3H-1λ3,2-benziodaoxole

We report on the effect of small side-chain modifications to the structure of 3,3-dimethyl-1-(trifluoromethyl)-3H-1λ3,2-benziodaoxole (1b) on its reactivity, as expressed by the initial rate v0 in a model reaction, and show how the latter can be successfully correlated to an easily determined physical parameter p, a 13C NMR chemical shift. The relationship v0～ p is already present in the simplest starting material devoid of the hypervalent bond and the iodine core and, therefore, presents an interesting approach towards the future scaffold-optimization of this class of reagents. The reactivity of hypervalent-iodine-based trifluoromethylating agents, as expressed by the initial rate v0 in a model reaction, correlates to an easily determined physical parameter p, a 13C NMR chemical shift.

Palladium-Aminopyridine Catalyzed C?H Oxygenation: Probing the Nature of Metal Based Oxidant

A mechanistic study of direct selective oxidation of benzylic C(sp3)?H groups with peracetic acid, catalyzed by palladium complexes with tripodal amino-tris(pyriylmethyl) ligands, is presented. The oxidation of arylalkanes having secondary and tertiary benzylic C?H groups, predominantly yields, depending on the substrate and conditions, either the corresponding ketones or alcohols. One of the three 2-pyriylmethyl moieties, which is pending in the starting catalyst, apparently, facilitates the active species formation and takes part in stabilization of the high-valent Pd center in the active species, occupying the axial coordination site of palladium. The catalytic, as well as isotopic labeling experiments, in combination with ESI-MS data and DFT calculations, point out palladium oxyl species as possible catalytically active sites, operating essentially via C?H abstraction/oxygen rebound pathway. For the ketones formation, O?H abstraction/в-scission mechanism has been proposed.

To Rebound or...Rebound? Evidence for the "alternative Rebound" mechanism in Ca'H Oxidations by the systems nonheme Mn Complex/H2O2/carboxylic acid

In this work, it has been shown that aliphatic Ca'H oxidations by bioinspired catalyst systems Mn aminopyridine complex/H2O2/carboxylic acid in acetonitrile afford predominantly a mixture of the corresponding alcohol and the ester. The alcohol/ester ratio is higher for catalysts bearing electron-donating groups at the aminopyridine core. Isotopic labeling studies witness that the oxygen atom of the alcohol originates from the H2O2molecule, while the ester oxygen comes exclusively from the acid. Oxidation of ethylbenzene in the presence of acetic acid affords enantiomerically enriched 1-phenylethanol and 1-phenyl acetate, with close enantioselectivities and the same sign of absolute chirality. Experimental data and density functional theory calculations provide evidence in favor of the rate-limiting benzylic H atom abstraction by the high-spin (S = 1) [LMnV(O)OAc]2+active species followed by competitive OH/OC(O)R rebound. This mechanism has been unprecedented for Ca'H oxidations catalyzed by bioinspired Mn complexes. The trends governing the alcohol/ester ratios have been rationalized in terms of steric properties of the catalyst, acid, and substrate. copy; 2021 American Chemical Society.

A one-pot two-step synthesis of tertiary alcohols combining the biocatalytic laccase/TEMPO oxidation system with organolithium reagents in aerobic aqueous media at room temperature

The one-pot/two-step combination of enzymes and polar organometallic chemistry in aqueous media is for the first time presented as a proof-of-concept study. The unprecedented combination of the catalytic oxidation of secondary alcohols by the system laccase/TEMPO with the ultrafast addition (3 s reaction time) of polar organometallic reagents (RLi/RMgX) to thein situformed ketones, run under air at room temperature, allows the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions (up to 96%).

Iron-catalysed 1,2-aryl migration of tertiary azides

1,2-Aryl migration of α,α-diaryl tertiary azides was achieved by using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr·HCl. The reaction generated aniline products in good yields after one-pot reduction of the migration-resultant imines.

Combination of organocatalytic oxidation of alcohols and organolithium chemistry (RLi) in aqueous media, at room temperature and under aerobic conditions

A tandem protocol to access tertiary alcohols has been developed which combines the organocatalytic oxidation of secondary alcohols to ketones followed by their chemoselective addition by several RLi reagents. Reactions take place at room temperature, under air and in aqueous solutions, a trio of conditions that are typically forbidden in polar organometallic chemistry.

Organophotoredox-Catalyzed Decarboxylative C(sp3)-O Bond Formation

This manuscript reports a visible-light-mediated organosulfide catalysis that enables the decarboxylative coupling between simple aliphatic alcohol and tertiary or secondary alkyl carboxylic acid-derived redox active esters to produce a C(sp3)-O-C(sp3) fragment. Results of the coupling using other heteroatom nucleophiles such as water, amides, and thiols are also described.

Harnessing the Power of the Asymmetric Grignard Synthesis of Tertiary Alcohols: Ligand Development and Improved Scope Exemplified by One-Step Gossonorol Synthesis

A series of N-substituted cyclohexyldiaminophenolic ligands for the asymmetric Grignard synthesis of tertiary alcohols is reported. The 2,5-dimethylpyrrole-decorated ligand led to improved enantioselectivities and broadened the scope of the methodology. As an exemplar, we report an unprecedented highly selective one-step synthesis of gossonorol in 93% ee, also constituting the shortest formal syntheses of natural products boivinianin B and yingzhaosu C.

Carbon Dioxide-Mediated C(sp2)-H Arylation of Primary and Secondary Benzylamines

C-C bond formation by transition metal-catalyzed C-H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of ortho-arylbenzylamines, however, effective ortho-C-C bond formation of free primary and secondary benzylamines using PdII remains an outstanding challenge. Presented herein is a new strategy for constructing ortho-arylated primary and secondary benzylamines mediated by carbon dioxide (CO2). The use of CO2 with Pd is critical to allowing this transformation to proceed under relatively mild conditions, and mechanistic studies indicate that it (CO2) is directly involved in the rate-determining step. Furthermore, the milder temperatures furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, an interesting chelate effect is shown to facilitate selective monoarylation.

Controllable Intramolecular Unactivated C(sp3)-H Amination and Oxygenation of Carbamates

Dual catalyst-controlled intramolecular unactivated C(sp3)-H amination and oxygenation of carbamates merging visible-light photocatalysis and earth-abundant transition metal catalysis have been reported. Useful amino alcohol and diol derivatives could be selectively obtained from readily available tertiary alcohol derivatives. The possible mechanisms have been proposed via a 1,5-HAT process followed by Lewis acid-controlled cyclization. The nickel and zinc catalysts inhibit the formation of oxygenation and amination products, respectively. An interesting phenomenon of chirality transfer is also observed.