18869-27-7

Upstream product

• 6006-68-4 (+/-)-1-cyclohexyl-2-phenylethanol 
• 144-62-7 oxalic acid 
• 4442-82-4 rac-2-cyclohexyl-1-phenylethan-1-ol 
• 100-42-5 styrene 
• 108-85-0 1-bromocyclohexane 
• 626-62-0 Cyclohexyl iodide 
• 1088-01-3 tricyclohexylborane 
• 40110-66-5 (E)-2-phenyl-1-(phenylsulfinyl)ethene 
• 536-74-3 phenylacetylene 
• 7664-93-9 sulfuric acid 
• 2043-61-0 cyclohexanecarbaldehyde 
• 667458-78-8 benzyl 3,5-bis(trifluoromethyl)phenyl sulfone 
• 100-39-0 benzyl bromide 
• 931-51-1 cyclohexylmagnesiumchloride 

Downstream Products

• 100971-60-6 2-cyclohexyl-3-phenyl-oxirane 
• 854219-91-3 1,2-dibromo-1-cyclohexyl-2-phenyl-ethane 
• 65-85-0 benzoic acid 
• 98-89-5 Cyclohexanecarboxylic acid 
• 61259-29-8 1-cyclohexyl-2-phenylethanone 
• 5653-09-8 2-cyclohexyl-1-phenylethan-1-one 
• 100863-32-9 1-cyclohexyl-2-phenyl-ethane-1,2-diol 
• 36677-65-3 1-cyclohexyl-2-phenylethane-1,2-dione 
• 712-50-5 Cyclohexyl phenyl ketone 
• 116544-25-3 trans-1-Cyclohexyl-2-phenyloxirane 

Relevant academic research and scientific papers

An Amine-Assisted Ionic Monohydride Mechanism Enables Selective Alkyne cis-Semihydrogenation with Ethanol: From Elementary Steps to Catalysis

The selective synthesis of Z-alkenes in alkyne semihydrogenation relies on the reactivity difference of the catalysts toward the starting materials and the products. Here we report Z-selective semihydrogenation of alkynes with ethanol via a coordination-induced ionic monohydride mechanism. The EtOH-coordination-driven Cl- dissociation in a pincer Ir(III) hydridochloride complex (NCP)IrHCl (1) forms a cationic monohydride, [(NCP)IrH(EtOH)]+Cl-, that reacts selectively with alkynes over the corresponding Z-alkenes, thereby overcoming competing thermodynamically dominant alkene Z-E isomerization and overreduction. The challenge for establishing a catalytic cycle, however, lies in the alcoholysis step; the reaction of the alkyne insertion product (NCP)IrCl(vinyl) with EtOH does occur, but very slowly. Surprisingly, the alcoholysis does not proceed via direct protonolysis of the Ir-C(vinyl) bond. Instead, mechanistic data are consistent with an anion-involved alcoholysis pathway involving ionization of (NCP)IrCl(vinyl) via EtOH-for-Cl substitution and reversible protonation of Cl- ion with an Ir(III)-bound EtOH, followed by β-H elimination of the ethoxy ligand and C(vinyl)-H reductive elimination. The use of an amine is key to the monohydride mechanism by promoting the alcoholysis. The 1-amine-EtOH catalytic system exhibits an unprecedented level of substrate scope, generality, and compatibility, as demonstrated by Z-selective reduction of all alkyne classes, including challenging enynes and complex polyfunctionalized molecules. Comparison with a cationic monohydride complex bearing a noncoordinating BArF- ion elucidates the beneficial role of the Cl- ion in controlling the stereoselectivity, and comparison between 1-amine-EtOH and 1-NaOtBu-EtOH underscores the fact that this base variable, albeit in catalytic amounts, leads to different mechanisms and consequently different stereoselectivity.

Dinuclear cobalt complex-catalyzed stereodivergent semireduction of alkynes: Switchable selectivities controlled by H2O

Catalytic semireduction of internal alkynes to alkenes is very important for organic synthesis. Although great success has been achieved in this area, switchable Z/E stereoselectivity based on a single catalyst for the semireduction of internal alkynes is a longstanding challenge due to the multichemo- and stereoselectivity, especially based on less-expensive earth-abundant metals. Herein, we describe a switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand. It was found that cis-reduction of the alkyne occurs first and the Z-E alkene stereoisomerization process is formally controlled by the amount of H2O, since the concentration of H2O may influence the catalytic activity of the catalyst for isomerization. Therefore, this protocol provides a facile way to switch to either the (Z)- or (E)-olefin isomer in a single transformation by adjusting the amount of water.

Visible-Light-Mediated C-I Difluoroallylation with an α-Aminoalkyl Radical as a Mediator

Herein, we report a protocol for direct visible-light-mediated C-I difluoroallylation reactions of α-trifluoromethyl arylalkenes with alkyl iodides at room temperature with an α-aminoalkyl radical as a mediator. The protocol permits efficient functionalization of various α-trifluoromethyl arylalkenes with cyclic and acyclic primary, secondary, and tertiary alkyl iodides and is scalable to the gram level. This mild protocol uses an inexpensive mediator and is suitable for late-stage functionalization of complex natural products and drugs.

A Solid-Phase Assisted Flow Approach to In Situ Wittig-Type Olefination Coupling

Described herein is the development of a continuous flow, solid-phase triphenylphosphine (PS-PPh3) assisted protocol to facilitate the in situ coupling of reciprocal pairs of halogen and carbonyl functionalised molecular pairs by a Wittig olefination within 15 mins. The protocol entails injecting a single solution (1 : 1 CHCl3 : EtOH) containing the halogenated and carbonyl-based substrates into a continuously flowing stream of CHCl3 : EtOH (1 : 1), passed through a fixed bed of K2CO3 and PS-PPh3. With advancement to the previous PS-PPh3 coupling procedures, the method employs a traditional polystyrene-based immobilisation matrix, the substrate scope of the protocol extended to substituted ketones, secondary alkyl chlorides, and an unprotected maleimide scaffold.

Visible-Light-Mediated Alkenylation of Alkyl Boronic Acids without an External Lewis Base as an Activator

Herein we report a protocol for the direct visible-light-mediated alkenylation of alkyl boronic acids at room temperature without an external Lewis base as an activator, and we propose a mechanism involving benzenesulfinate activation of the alkyl boronic acids. The protocol permits the efficient functionalization of a broad range of cyclic and acyclic primary and secondary alkyl boronic acids with various alkenyl sulfones. We demonstrated its utility by preparing or functionalizing several pharmaceuticals and natural products.

Wittig Olefination Using Phosphonium Ion-Pair Reagents Incorporating an Endogenous Base

Despite common perception, the use of strong bases in Wittig chemistry is utterly unnecessary: we report a series of novel ion-pair phosphonium carboxylate reagents which are essentially "storable ylides". These reagents are straightforwardly prepared in excellent yields, and their fluxional nature permits clean olefination of a broad range of aldehydes and even hemiacetals.

Photoinduced copper-catalyzed dual decarboxylative coupling of α,β-unsaturated carboxylic acids with redox-active esters

The first photoinduced copper-catalyzed dual decarboxylative cross-coupling of α,β-unsaturated carboxylic acids and redox-active esters has been developed. This reaction enabled C(sp2)–C(sp3) bond formation, which afforded a variety of synthetically valuable alkene derivatives. Many α,β-unsaturated carboxylic acids and redox-active ester derivatives were tolerant to this reaction. The reaction also tolerated many common functional groups.

Copper porphyrin-catalyzed cross dehydrogenative coupling of alkanes with carboxylic acids: Esterification and decarboxylation dual pathway

A dual-functional copper porphyrin-catalyzed cross dehydrogenative coupling (CDC) of carboxylic acids with alkanes was reported firstly. The reaction gives allylic esters or alkylalkenes depending on the carboxylic acid substrates. Copper porphyrin catalyzed CDC method has the superiority of short reaction time, good functional group tolerance, base and solvent free, producing target products in an atom-economic manner.

Photoinduced Deaminative Coupling of Alkylpyridium Salts with Terminal Arylalkynes

A novel and simple Z-alkene synthesis by the photocatalyzed coupling reactions of alkylpyridium salts, which were prepared from primary amines, with terminal aryl alkynes at room temperature is reported here. A wide range of primary amines, which contain different functional groups, were tolerated under these conditions. The mild reaction conditions, broad substrate scope, functional group tolerance, and operational simplicity make this deaminative coupling reaction a valuable method in organic syntheses.

Stereoselective Chromium-Catalyzed Semi-Hydrogenation of Alkynes

Chromium complexes have found very little applications as hydrogenation catalysts. Here, we report a Cr-catalyzed semi-hydrogenation of internal alkynes to the corresponding Z-alkenes with good stereocontrol (up to 99/1 for dialkyl alkynes). The catalyst comprises the commercial reagents chromium(III) acetylacetonate, Cr(acac)3, and diisobutylaluminium hydride, DIBAL?H, in THF. The semi-hydrogenation operates at mild conditions (1-5 bar H2, 30 °C).