33284-74-1

Upstream product

• 537-35-9 1,2-Disyringylethane 
• 15332-24-8 3,3',4,4',5,5'-hexamethoxystilbene 
• 21852-50-6 3,4,5-trimethoxybenzyl bromide 
• 69404-94-0 O-tert-butyldimethylsilylvanillin 
• 97315-18-9 p-methoxy-m-(tert-butyldimethylsilyloxy)-benzaldehyde 
• 61240-22-0 dehydrobrittonin A 
• 86-81-7 3,4,5-trimethoxy-benzaldehyde 
• 124-38-9 carbon dioxide 
• 3840-30-0 5-(chloromethyl)-1,2,3-trimethoxybenzene 
• 60095-69-4 [1-(3,5-Bis-benzyloxy-phenyl)-meth-(Z)-ylidene]-(2,2-diethoxy-ethyl)-amine 
• 67-56-1 methanol 
• 72092-48-9 3,4,5-trimethoxybenzyl acetate 
• 157843-82-8 3,4,5-Trimethoxybenzyl pivalate 
• 3840-31-1 (3,4,5-trimethoxyphenyl)methanol 

Relevant academic research and scientific papers

Direct Hydrodecarboxylation of Aliphatic Carboxylic Acids: Metal- and Light-Free

A mild and inexpensive method for direct hydrodecarboxylation of aliphatic carboxylic acids has been developed. The reaction does not require metals, light, or catalysts, rendering the protocol operationally simple, easy to scale, and more sustainable. Crucially, no additional H atom source is required in most cases, while a broad substrate scope and functional group tolerance are observed.

Reactions of benzyltriphenylphosphonium salts under photoredox catalysis

The development of benzyltriphenylphosphonium salts as alkyl radical precursors using photoredox catalysis is described. Depending on substituents, the benzylic radicals may couple to form C-C bonds or abstract a hydrogen atom to form C-H bonds. A natural product, brittonin A, was also synthesized using this method.

Molybdenum-Catalyzed Deoxygenation Coupling of Lignin-Derived Alcohols for Functionalized Bibenzyl Chemicals

With the growing demand for sustainability and reducing CO2 footprint, lignocellulosic biomass has attracted much attention as a renewable, carbon-neutral and low-cost feedstock for the production of chemicals and fuels. To realize efficient utilization of biomass resource, it is essential to selectively alter the high degree of oxygen functionality of biomass-derivates. Herein, we introduced a novel procedure to transform renewable lignin-derived alcohols to various functionalized bibenzyl chemicals. This strategy relied on a short deoxygenation coupling pathway with economical molybdenum catalyst. A well-designed H-donor experiment was performed to investigate the mechanism of this Mo-catalyzed process. It was proven that benzyl carbon-radical was the most possible intermediate to form the bibenzyl products. It was also discovered that the para methoxy and phenolic hydroxyl groups could stabilize the corresponding radical intermediates and then facilitate to selectively obtain bibenzyl products. Our research provides a promising application to produce functionalized aromatics from biomass-derived materials.

Ni-Catalyzed Iterative Alkyl Transfer from Nitrogen Enabled by the in Situ Methylation of Tertiary Amines

Current methods to achieve transition-metal-catalyzed alkyl carbon-nitrogen (C-N) bond cleavage require the preformation of ammonium, pyridinium, or sulfonamide derivatives from the corresponding alkyl amines. These activated substrates permit C-N bond cleavage, and their resultant intermediates can be intercepted to affect carbon-carbon bond-forming transforms. Here, we report the combination of in situ amine methylation and Ni-catalyzed benzalkyl C-N bond cleavage under reductive conditions. This method permits iterative alkyl group transfer from tertiary amines and demonstrates a deaminative strategy for the construction of Csp3-Csp3 bonds. We demonstrate PO(OMe)3 (trimethylphosphate) to be a Ni-compatible methylation reagent for the in situ conversion of trialkyl amines into tetraalkylammonium salts. Single, double, and triple benzalkyl group transfers can all be achieved from the appropriately substituted tertiary amines. Transformations developed herein proceed via recurring events: The in situ methylation of tertiary amines by PO(OMe)3, Ni-catalyzed C-N bond cleavage, and concurrent Csp3-Csp3 bond formation.

Ruthenium nanoparticle-intercalated montmorillonite clay for solvent-free alkene hydrogenation reaction

Well-characterized, ruthenium nanoparticle-intercalated montmorillonite clay was used as a catalyst in solvent-free alkene hydrogenation reactions and the corresponding products were obtained in good yields. The catalytic activity of ruthenium nanoparticle-intercalated montmorillonite clay was successfully tested with 16 different functionalized and non-functionalized alkenes. Apart from alkene reduction, the ruthenium nanoparticle-intercalated montmorillonite clay was also tested in Wittig-type reactions for obtaining dehydrobrittonin A, an important intermediate for the synthesis of brittonin A. Ruthenium nanoparticle-intercalated montmorillonite clay was found to be active in the synthesis of dehydrobrittonin A and brittonin A. The ability to recycle the catalyst nine times, together with low catalyst loading, high catalytic activity and catalytic selectivity were noteworthy advantages of the proposed protocol.

Homocoupling versus reduction of radicals: An experimental and theoretical study of Ti(iii)-mediated deoxygenation of activated alcohols

A detailed experimental and theoretical study corroborates that the reductive deoxygenation of activated (allylic or benzylic) alcohols with excess Ti(iii) proceeds via an allyl(benzyl)-radical and allyl(benzyl)-Ti, which is protonated, regioselectively in the case of allylic derivatives. The H atom of the newly formed C-H bond in the product originates from the -OH group of the starting material. The deoxygenation of lithium alkoxides or alcohols by using 1.0 mol of Ti(iii) leads to the corresponding dimerization products in good yields. An excellent agreement with the experimental data was obtained by using a reaction kinetics simulator to discriminate between competing reactions.

General Ambient Temperature Benzylic Metalations Using Mixed-Metal Li/K-TMP Amide

Highly regioselective benzylic metalations in hydrocarbon solvent have been achieved at rt and 0 °C using a mixed-metal Li/K-TMP amide comprised of KOtBu, BuLi, and 2,2,6,6,-tetramethylpiperidine (TMP(H)). Mixing of KOtBu, BuLi, and TMP(H) in heptane gave a solution of the base mixture which when used in deuterium labeling experiments confirmed the requirement of the three reagent components for both reactivity and selectivity. The reaction protocol is operationally straightforward and found to be applicable to a broad range of substrates. Upon generation of the metalated products, they are reacted in heptane at ambient temperature in a variety of synthetically useful ways. Illustrated examples include generation of the benzyltrimethylsilanes and α,α-bis(trimethylsilyl)toluenes reagents, which are bench-stable surrogates of benzyl anions and α-silyl carbanions utilized for nucleophilic addition and Peterson olefination reactions. Direct C-C couplings mediated by 1,2-dibromoethane provided entries into bibenzyls and [2.2]metacyclophanes. Comparison of reaction outcomes with the same reactions carried out in THF at -78 °C showed no negative effects for conducting the reactions under these milder more user-friendly conditions.

Ti-catalyzed homolytic opening of ozonides: A sustainable C-C bond-forming reaction

The unprecedented homolytic opening of ozonides promoted and catalyzed by titanocene(III) is reported. This novel reaction proceeds at room temperature under neutral, mild conditions compatible with many functional groups and provides carbon radicals suitable to form C-C bonds via both homocoupling and cross-coupling processes. The procedure has been advantageously exploited for the straightforward synthesis of the natural product brittonin A.

Homo- and hetero-oxidative coupling of benzyl anions

The regioselective benzylic metalation of substituted toluenes using BuLi/KO-t-Bu/TMP(H) (LiNK metalation conditions) with subsequent in situ oxidative C-C coupling has been developed for the facile generation of 1,2-diarylethanes. A range of oxidants can be used for the oxidative coupling step, with 1,2-dibromoethane proving optimal. Heterocouplings can be achieved starting from a mixture of two different toluenes with a bias toward cross coupling achievable by using a 2-fold excess of one toluene starting material. The utility of this approach is illustrated by the synthesis of several biologically active natural products. A distinct advantage is that the synthetic steps typically required to preactivate the coupling substrates are eliminated and no transition metal is required to facilitate the C-C bond formation.

Transfer hydrogenation of olefins catalysed by nickel nanoparticles

Nickel nanoparticles have been found to effectively catalyse the hydrogen-transfer reduction of a variety of non-functionalised and functionalised olefins using 2-propanol as the hydrogen donor. The heterogeneous process has been shown to be highly chemoselective for certain substrates, with all the corresponding alkanes being obtained in high yields. A synthesis of the natural dihydrostilbene brittonin A?is also reported based on the use of nickel nanoparticles.