15601-30-6

Upstream product

• 111-83-1 1-bromo-octane 
• 140-29-4 phenylacetonitrile 
• 75-86-5 2-hydroxy-2-methylpropanenitrile 
• 111-87-5 octanol 

Downstream Products

• 87184-49-4 N-(t-Butyldimethylsilyl)-n-octyl-phenylketenimin 
• 1081-77-2 n-nonylbenzene 
• 54835-31-3 2-Phenyl-2-phenylsulfanyl-decanenitrile 
• 100411-83-4 2,N-diphenyl-decanamidine 

Relevant academic research and scientific papers

Nickel-Catalyzed Migratory Hydrocyanation of Internal Alkenes: Unexpected Diastereomeric-Ligand-Controlled Regiodivergence

A regiodivergent nickel-catalyzed hydrocyanation of a broad range of internal alkenes involving a chain-walking process is reported. When appropriate diastereomeric biaryl diphosphite ligands are applied, the same starting materials can be converted to either linear or branched nitriles with good yields and high regioselectivities. DFT calculations suggested that the catalyst architecture determines the regioselectivity by modulating electronic and steric interactions. In addition, moderate enantioselectivities were observed when branched nitriles were produced.

METHOD FOR PRODUCING NITRILE COMPOUND

PROBLEM TO BE SOLVED: To provide a method whereby, while using a catalyst that contains a transition metal and can be relatively easily synthesized, even with a small amount of the transition metal, a nitrile compound can be produce efficiently by the α-alkylation of the nitrile compound. SOLUTION: A method includes the steps of: causing a nitrile compound having a nitrile-containing group represented by formula (1) and a primary alcohol compound represented by formula (2) to react with each other in a reaction liquid containing a transition metal nanoparticle of at least one of a ruthenium nanoparticle or a palladium nanoparticle, a base and a solvent, to produce a nitrile compound having a nitrile-containing group represented by formula (3). SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT

Atmosphere-Controlled Chemoselectivity: Rhodium-Catalyzed Alkylation and Olefination of Alkylnitriles with Alcohols

The chemoselective alkylation and olefination of alkylnitriles with alcohols have been developed by simply controlling the reaction atmosphere. A binuclear rhodium complex catalyzes the alkylation reaction under argon through a hydrogen-borrowing pathway and the olefination reaction under oxygen through aerobic dehydrogenation. Broad substrate scope is demonstrated, permitting the synthesis of some important organic building blocks. Mechanistic studies suggest that the alkylation product may be formed through conjugate reduction of an alkene intermediate by a rhodium hydride, whereas the formation of olefin product may be due to the oxidation of the rhodium hydride complex with molecular oxygen.

POP-pincer ruthenium complexes: D6 counterparts of osmium d 4 species

A wide range of ruthenium complexes stabilized by the POP-pincer ligand xant(PiPr2)2 (9,9-dimethyl-4,5- bis(diisopropylphosphino)xanthene) were prepared starting from cis-RuCl 2{κ-S-(DMSO)4} (1; DMSO = dimethyl sulfoxide). Treatment of toluene solutions of this adduct with the diphosphine under reflux leads to RuCl2{xant(PiPr2)2} (κ-S-DMSO) (2), which reacts with H2 in the presence of a Bronsted base. The reaction in the presence of Et3N affords RuHCl{xant(PiPr2)2}(κ-S-DMSO) (3), whereas NaH removes both chloride ligands to give RuH2{xant(P iPr2)2}(κ-S-DMSO) (4). The stirring of 3 in 2-propanol under 3 atm of H2 for a long time produces the elimination of DMSO and the coordination of H2 to yield the dihydrogen derivative, RuHCl(η2-H2){xant(P iPr2)2} (5). In contrast to H2, PPh3 easily displaces DMSO from the metal center of 3 to afford RuHCl{xant(PiPr2)2}(PPh3) (6), which can be also obtained starting from RuHCl(PPh3)3 (7) and xant(PiPr2)2. In contrast to 3, complex 4 does not undergo DMSO elimination to give RuH2(η2-H 2){xant(PiPr2)2} (8) under a H 2 atmosphere. However, the latter can be prepared by hydrogenation of Ru(COD)(COT) (9; COD = 1,5-cyclooctadiene and COT = 1,3,5-cyclooctatriene) in the presence of xant(PiPr2)2. A more efficient procedure to obtain 8 involves the sequential hydrogenation with ammonia borane of the allenylidene derivative RuCl2(i=Ci=Ci=CPh2) {xant(PiPr2)2} (10), which is formed from the reaction of 2 with 1,1-diphenyl-2-propyn-1-ol. The hydrogenation initially gives RuCl2(i=Ci=CHCHPh2){xant(PiPr 2)2} (11), which undergoes the subsequent reduction of the Ru-C double bond to yield the hydride-tetrahydroborate complex, RuH(η2-H2BH2){xant(PiPr 2)2} (12). The osmium complex, OsCl 2{xant(PiPr2)2}(κ-S-DMSO) (13), reacts with 1,1-diphenyl-2-propyn-1-ol in a similar manner to its ruthenium counterpart 2 to yield the allenylidene derivative, OsCl 2(i=Ci=Ci=CPh2){xant(PiPr2) 2} (14). Ammonia borane also reduces the Cβ-C γ double bond of the allenylidene of 14. However, the resulting vinylidene species, OsCl2(i=Ci=CHCHPh2){xant(P iPr2)2} (15), is inert. Complex 12 is an efficient catalyst precursor for the hydrogen transfer from 2-propanol to ketones, the α-alkylations of phenylacetonitrile and acetophenone with alcohols, and the regio- and stereoselective head-to-head (Z) dimerization of terminal alkynes.

Nickel-catalyzed hydrogenolysis of unactivated carbon-cyano bonds

Selective hydrogenolysis of C-CN bonds can allow chemists to take advantage of ortho-directing ability, α-C-H acidity and electron withdrawing ability of the cyano group for synthetic manipulations. We have discovered hydrogenolysis of aryl and aliphatic cyanides under just 1 bar of hydrogen by using a nickel catalyst. This protocol was applied in the aryl cyanide directed functionalization reaction and α-substitution of benzyl cyanides.

Osmium catalyst for the borrowing hydrogen methodology: α-alkylation of arylacetonitriles and methyl ketones

Complex [Os(η6-p-cymene)(OH)(IPr)]OTf is an efficient catalyst precursor for the α-alkylation of arylacetonitriles and methyl ketones with alcohols, which works with turnover frequencies between 675 and 176 h-1 for nitriles and between 194 and 28 h-1 for ketones.

Oxidative Decyanation of Secondary Nitriles to Ketones

Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.