94823-85-5Relevant academic research and scientific papers
Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5-Diaza-3,7-diphosphacyclooctane Ligand
Isbrandt, Eric S.,Nasim, Amrah,Newman, Stephen G.,Zhao, Karen
supporting information, p. 14646 - 14656 (2021/09/18)
We report a catalytic method to access secondary alcohols by the coupling of aryl iodides. Either aldehydes or alcohols can be used as reaction partners, making the transformation reductive or redox-neutral, respectively. The reaction is mediated by a Ni catalyst and a 1,5-diaza-3,7-diphosphacyclooctane. This P2N2ligand, which has previously been unrecognized in cross-coupling and related reactions, was found to avoid deleterious aryl halide reduction pathways that dominate with more traditional phosphines and NHCs. An interrupted carbonyl-Heck type mechanism is proposed to be operative, with a key 1,2-insertion step forging the new C-C bond and forming a nickel alkoxide that may be turned over by an alcohol reductant. The same catalyst was also found to enable synthesis of ketone products from either aldehydes or alcohols, demonstrating control over the oxidation state of both the starting materials and products.
Rhodium-Catalyzed Aldehyde Arylation via Formate-Mediated Transfer Hydrogenation: Beyond Metallic Reductants in Grignard/Nozaki-Hiyami-Kishi-Type Addition
Swyka, Robert A.,Zhang, Wandi,Richardson, Jeffery,Ruble, J. Craig,Krische, Michael J.
supporting information, p. 1828 - 1832 (2019/02/14)
The first intermolecular carbonyl arylations via transfer hydrogenative reductive coupling are described. Using rhodium catalysts modified by tBu2PMe, sodium formate-mediated reductive coupling of aryl iodides with aldehydes occurs in a chemoselective fashion in the presence of protic functional groups and lower halides. This work expands the emerging paradigm of transfer hydrogenative coupling as an alternative to pre-formed carbanions or metallic reductants in C=X addition.
Alkylation of aromatic aldehydes with alkylboron chloride derivatives
Kabalka, George W,Wu, Zhongzhi,Ju, Yuhong
, p. 1663 - 1670 (2007/10/03)
The reaction of aryl aldehydes with alkylboron chlorides has been investigated. Monoalkylboron dichlorides react with aryl aldehydes in hexane under reflux conditions to give a mixture of dichloroarylmethane and benzyl chloride. Under the same reaction conditions, dialkylboron chlorides lead to formation of a mixture of benzyl chloride and the chloroalkylation product. In the presence of a base such as 2,6-lutidine, the reactions of monoalkylboron dichlorides with aryl aldehydes yield small amounts of the desired alkylation products at room temperature. Dialkylboron chlorides react with aryl aldehydes in hexane in the presence of base to generate the corresponding arylalkylmethanols in good yields.
1-Naphthylcarbene: Spectroscopy, Kinetics, and Mechanisms
Barcus, R. L.,Hadel, L. M.,Johnston, L. J.,Platz, M. S.,Savino, T. G.,Scaiano, J. C.
, p. 3928 - 3937 (2007/10/02)
The reactions of 1-naphthylcarbene have been examined by using laser flash photolysis techniques.Generation of the carbene from the diazo precursor in hydrocarbon solvents leads to the formation of 1-naphthylmethyl radicals, which were characterized by their absorption at 363 nm.However, product studies in cyclohexane and cyclohexane-d12 reveal that the main reaction path is carbene insertion into the C-H bond rather than H abstraction. 1-Naphthylcarbene reacts readily with nitriles to yield nitrile ylides which can also be generated from the corresponding azirine.For example, the carbene reacts with acetonitrile with a rate constant of 4.6 X 1E5 M-1s-1 at 300 K to yield an ylide that can be trapped readily with electron-deficient olefins, such as diethyl fumarate.Reaction of the carbene with oxygen (k = 3.5 X 1E9 M-1 s-1) yields the carbonyl oxide (λmax 435 nm).Other reactions examined include halogen abstraction, addition to ketones, and reactions with triethylamine, pyridine, and ethers.The absolute kinetics of the various reactions were examined by monitoring the formation of the products (e.g., ylides, radicals, etc.), since the carbene spectrum was not detected directly.
