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Upstream product

• 1462-12-0 diethyl ethylidenemalonate 
• 626-62-0 Cyclohexyl iodide 
• 24371-94-6 cyclohexylmercury chloride 
• 446065-11-8 cyclohexyltrifluoro-λ⁴-borane potassium salt 
• 125764-09-2 tetraethylammonium bis<α,α-bis(trifluoromethyl)benzenemethanolato(2-)-C²,O>cyclohexylsilicate 
• 4441-56-9 cyclohexylboronic acid 
• 100-49-2 cyclohexylmethyl alcohol 
• 1569-69-3 Cyclohexanethiol 
• 2043-61-0 cyclohexanecarbaldehyde 
• 98-89-5 Cyclohexanecarboxylic acid 
• 13592-76-2 diethyl 2-(cyclohexylmethylene)malonate 
• 1184-58-3 dimethylaluminum chloride 

Relevant academic research and scientific papers

Photo-Mediated Decarboxylative Giese-Type Reaction Using Organic Pyrimidopteridine Photoredox Catalysts

The decarboxylative Giese-type reaction offers a versatile methodology for the radical alkylation of electron-deficient alkenes. Photo-mediated variants often require a pre-activation of carboxylic acids and/or employment of costly transition-metal photocatalysts. Herein, we present a metal-free photocatalyzed decarboxylative Giese-type addition to electron-deficient alkenes using pyrimidopteridine N-oxides as organic photoredox-active catalysts. This protocol comprises mono-, di-, and trisubstituted aliphatic, α-amino, and α-oxy acids as well as a variety of electron-deficient alkenes. Moreover, post-synthetic derivatization and applications are presented.

Photocatalytic Giese-Type Reaction with Alkylsilicates Bearing C,O-Bidentate Ligands

Herein, a photocatalytic Giese-type reaction with alkylsilicates bearing C,O-bidentate ligands as stable alkyl radical precursors has been reported. The alkylsilicates were prepared in one step from organometallic reagents. Not only primary, secondary, and tertiary alkyl radicals, but also elusive methyl radicals, could be generated by using the present reaction system. The generated radicals were trapped by electron-deficient olefins bearing various functional groups to give the desired alkyl adducts. The silicon byproduct can be recovered after the photoreaction. The radical generation process was investigated by theoretical calculations, which provided an insight into the facile generation of methyl radicals from methylsilicate bearing C,O-bidentate ligands.

General access to C-centered radicals: Combining a bioinspired photocatalyst with boronic acids in aqueous media

Carbon-centered radicals are indispensable building blocks for modern synthetic chemistry. In recent years, visible light photoredox catalysis has become a promising avenue to access C-centered radicals from a broad array of latent functional groups, including boronic acids. Herein, we present an aqueous protocol wherein water features a starring role to help transform aliphatic, aromatic, and heteroaromatic boronic acids to C-centered radicals with a bioinspired flavin photocatalyst. These radicals are used to deliver a diverse pool of alkylated products, including three pharmaceutically relevant compounds, via open-shell conjugate addition to disparate Michael acceptors. The mechanism of the reaction is investigated by computational studies, deuterium labeling, radical-trapping experiments, and spectroscopic analysis.

Iridium complex-linked porous organic polymers for recyclable, broad-scope photocatalysis of organic transformations

Two rigid porous organic polymers (Ir-POP-1 and Ir-POP-2) were prepared from the coupling reactions of tetraphenylmethane tetraborate and two [Ir(ppy)2(dtbbpy)]+-based bitopic linkers and applied as heterogeneous visible-light photocatalysts for organic transformations. Ir-POP-2 was found to exhibit high catalytic activity for a wide range of organic reactions, which include Smiles-Truce rearrangement of alkyliodides, desulfurative conjugate addition to Michael acceptors, and aerobic oxidations of sulfides and arylboronic acids. For all the transformations, Ir-POP-2 could achieve heterogeneous photocatalytic efficiency that rivals that of the homogeneous prototype iridium complexes. This remarkably high photocatalytic performance has been attributed to the large pore size of the conjugated backbone. The new heterogeneous photocatalyst was also highly stable to achieve good recyclability for all the studied reactions and could be reused eight to nineteen times.

Dehydroxymethylation of alcohols enabled by cerium photocatalysis

Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.

Dehydroxymethylation of Alcohols Enabled by Cerium Photocatalysis

Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.

Alkyl radical precursor and application thereof in establishing C-C bond

The invention provides a precursor for generating an alkyl radical based on the visible light induction and a novel method for generating the radical. The alkyl sulfenamide is used as the radical precursor to generate the alkyl radical by virtue of the C-S bond cracking accelerated by the visible light, and then the alkyl radical is applied to the chemical reaction for establishing a C-C bond. Thereaction system has the characteristic of high efficiency, and has important scientific significance and application value for researching the novel C-C bond formation reaction, organic synthesis, drug synthesis and the like. In general, the invention provides a novel general method having practical application value. The thioalcohol (thioether) with rich resources is converted to a tool for derivating the alkyl radical.

A Desulfurative Strategy for the Generation of Alkyl Radicals Enabled by Visible-Light Photoredox Catalysis

Herein, we present a new desulfurative method for generating primary, secondary, and tertiary alkyl radicals through visible-light photoredox catalysis. A process that involves the generation of N-centered radicals from sulfinamide intermediates, followed by subsequent fragmentation, is critical to forming the corresponding alkyl radical species. This strategy has been successfully applied to conjugate addition reactions that features mild reaction conditions, broad substrate scope (>60 examples), and good functional-group tolerance.

Decarboxylative Giese-Type Reaction of Carboxylic Acids Promoted by Visible Light: A Sustainable and Photoredox-Neutral Protocol

We describe herein a transition-metal-free method for the decarboxylative generation of radicals from carboxylic acids and their 1,4-addition to Michael acceptors. The Fukuzumi catalyst (9-mesitylene-10-methylacridinium perchlorate, [Acr-Mes]ClO4) enabled this transformation under visible-light irradiation at room temperature with CO2 as the only byproduct. The scope and limitations of this protocol were examined by using a range of Michael acceptors (15 examples) and carboxylic acids (18 examples). The use of 3-hydroxypivalic acid in this protocol allowed the straightforward formation of a diastereomerically pure δ-lactone. Moreover, when a homoallylic acid was used, a radical cascade reaction took place with the formation of three C–C bonds.

Hypervalent iodine(III) catalyzed radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes under photolysis

Hypervalent iodine(III) catalyzed diastereoselective radical hydroacylation of alkylidenemalonates bearing (?)-8-phenylmenthol as a chiral auxiliary with aliphatic aldehydes is realized under photolysis. This work represent the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The reaction is initiated by the photolysis of hypervalent iodine(III) catalyst under mild and metal-free conditions. The synthetic potential of this methodology was demonstrated by the short formal synthesis of (?)-methyleneolactocin.