26110-92-9

Upstream product

• 6013-92-9 1-(4-methoxyphenyl)-2,2-dimethylpropan-1-ol 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 3282-30-2 pivaloyl chloride 
• 2040-26-8 1-(4-methoxyphenyl)-2,2-dimethyl-1-propanone 
• 15501-33-4 neopentyl iodide 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 753-89-9 neopentyl chloride 
• 677-22-5 tert-butylmagnesium chloride 
• 132381-64-7 C₂₁H₁₈O₂S 
• 86439-85-2 DL-3,4-Bis(4-methoxyphenyl)-2,2,5,5-tetramethylhexan 
• 345941-79-9 meso-3,4-Bis(4-methoxyphenyl)-2,2,5,5-tetramethylhexan 
• 507-19-7 t-butyl bromide 
• 824-94-2 p-methoxybenzyl chloride 
• 105-13-5 4-Methoxybenzyl alcohol 

Relevant academic research and scientific papers

Copper-catalyzed sp3-sp3 cross-coupling of turbo grignards with benzyl halides

The aromatic ring in benzyl halides and sulfonates imparts unique reactivity at the benzylic carbon atom. Photoredox sp3-sp3 cross-coupling proved ineffective for coupling p-methoxybenzyl chloride (PMBCl), leading to a new strategy for the sp3-sp3 cross-coupling of benzyl halides and sulfonates. This strategy involved LiCl-accelerated synthesis of a Grignard reagent followed by a copper-catalyzed cross-coupling. The conditions worked well for PMBCl due to its exceptional reactivity but other benzyl bromides or sulfonates reacted poorly.

Thermal Rearrangement of Sulfamoyl Azides: Reactivity and Mechanistic Study

The rearrangement of sulfamoyl azides under thermal conditions to form a C-C bond while breaking two C-N bonds is reported. Mechanistic study shows that this reaction goes through a Curtius-type rearrangement to form a 1,1-diazene, then which rearranges possibly through both a concerted rearrangement process and a stepwise radical process. This rearrangement could be used in the synthesis of complex biologically active molecules, such as sterols, and piperine derivatives.

Cross-coupling of non-activated chloroalkanes with aryl grignard reagents in the presence of iron/N-heterocyclic carbene catalysts

An efficient and high-yielding cross-coupling reaction of various primary, secondary, and tertiary alkyl chlorides with aryl Grignard reagents was achieved by using catalytic amounts of N-heterocyclic carbene ligands and iron salts. This reaction is a simple and efficient arylation method having applicability to a wide range of industrially abundant chloroalkanes, including polychloroalkanes, which are challenging substrates under conventional cross-coupling conditions.

Cross-coupling of grignard reagents with sulfonyl-activated sp3 carbon-nitrogen bonds

Sulfonyl-activated sp3 carbon-nitrogen bonds have been found to be cleaved by Grignard reagents in the presence of 5 mol% of copper(I) iodide (CuI). Significantly, a broad range of sulfonyl-activated benzylic, allylic, and propargylic amines smoothly undergo the cross-coupling reaction with Grignard reagents to afford structurally diverse coupling products in good to excellent yields and with high chemo-, regio-, and stereoselectivity. Moreover, an S N2 mechanism has been demonstrated to be involved in the cross-coupling reaction that allows the asymmetric synthesis of chiral hydrocarbons from optically active α-branched amine derivatives. Copyright

Photochemistry of substituted benzyl acetates and benzyl pivalates: A reinvestigation of substituent effects

The photosolvolysis reactions, in methanol, of six substituted benzyl acetates (7a-f) and benzyl pivalates (8a-f) were studied. Five major benzylic products were formed from two critical intermediates. The ethers (9) were formed from the ion pair, 15, and all of the other products (10-14) were formed from the radical pair, 16. Quenching studies showed that only excited singlet state reactivity was important. The product yields were found to be highly substituent dependent. For instance, for the acetate esters, the yield of ether (9) varied from 2% for X = 4-OCH3 to 32% for X = 3-OCH3. Most of the differences in the yields could be attributed to ground state processes that occur after bond cleavage. The important competition is between electron transfer, converting the radical pair to the ion pair, and decarboxylation of RCO2*. The rates of electron transfer are shown to fit Marcus theory in both the normal and inverted regions. Direct heterolytic cleavage to form the ion pair is of minimal importance.

Nickel-catalyzed cross-coupling of unactivated neopentyl iodides with Grignard reagents

Primary neopentyl iodides react with aryl Grignard reagents in the presence of 10 mol% (dppf)NiCl2 to give the cross-coupled product.

Radical Substitution on the Sulphur of Thioester Group

Intermolecular reaction of an organo-radical with thioester gives the sulphide, which is formed by the sulphur centred substitution of acyl groups with a nucleophilic organo-radical, but no displacement of S-alkyl groups with the organo-radical takes place.

Thermolabile Hydrocarbons, XVIII. 1-Substituted Neopentyl radicals and their Dimers

Five 3,4-diaryl-2,2,5,5-tetramethylhexanes 1a - e were prepared as pure meso- and DL-isomers.According to the NMR spectra, x-ray analyses for meso- and DL-1e (with an (FB)2E conformation as energy minimum for DL-1e), and force field calculations the diastereomers have distinctly different minimum energy conformations, rotational potentials, and strain enthalpies.Also the activation parameters for the thermal dissociation into 1-arylneopentyl radicals 2 are typically differing.From an entropy discussion it is concluded that sandwich-like diastereomeric radical complexes are formed in these reactions as first intermediates.Their tightness influences ΔS%.The recombinations of the radicals 2 likewise take place stereoselectively.Their substituent effects on the selectivity can also be understood by primary formation of diastereomeric complexes of radical pairs.