57494-03-8Relevant academic research and scientific papers
Palladium-Catalyzed Synthesis of α-Methyl Ketones from Allylic Alcohols and Methanol
Biswal, Priyabrata,Samser, Shaikh,Meher, Sushanta Kumar,Chandrasekhar, Vadapalli,Venkatasubbaiah, Krishnan
supporting information, p. 413 - 419 (2021/11/01)
One-pot synthesis of α-methyl ketones starting from 1,3-diaryl propenols or 1-aryl propenols and methanol as a C1 source is demonstrated. This one-pot isomerization-methylation is catalyzed by commercially available Pd(OAc)2 with H2O as the only by-product. Mechanistic studies and deuterium labelling experiments indicate the involvement of isomerization of allyl alcohol followed by methylation through a hydrogen-borrowing pathway in these isomerization-methylation reactions.
Experimental and Computational Studies of Palladium-Catalyzed Spirocyclization via a Narasaka-Heck/C(sp3or sp2)-H Activation Cascade Reaction
Wei, Wan-Xu,Li, Yuke,Wen, Ya-Ting,Li, Ming,Li, Xue-Song,Wang, Cui-Tian,Liu, Hong-Chao,Xia, Yu,Zhang, Bo-Sheng,Jiao, Rui-Qiang,Liang, Yong-Min
supporting information, p. 7868 - 7875 (2021/05/27)
The first synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem Narasaka-Heck/C(sp3 or sp2)-H activation reaction is reported here. The key step in this transformation is the activation of a δ-C-H bond via an in situ generated σ-alkyl-Pd(II) species to form a five-membered spiro-palladacycle intermediate. The concerted metalation-deprotonation (CMD) process, rate-determining step, and energy barrier of the entire reaction were explored by density functional theory (DFT) calculations. Moreover, a series of control experiments was conducted to probe the rate-determining step and reversibility of the C(sp3)-H activation step.
Iron-Catalyzed Cleavage Reaction of Keto Acids with Aliphatic Aldehydes for the Synthesis of Ketones and Ketone Esters
Zhou, Fangyuan,Li, Lesong,Lin, Kao,Zhang, Feng,Deng, Guo-Jun,Gong, Hang
supporting information, p. 4246 - 4250 (2020/03/11)
The radical–radical coupling reaction is an important synthetic strategy. In this study, the iron-catalyzed radical–radical cross-coupling reaction based on the decarboxylation of keto acids and decarbonylation of aliphatic aldehydes to obtain valuable aryl ketones is reported for the first time. Remarkably, when tertiary aldehydes were used as carbonyl sources, ketone esters were selectively obtained instead of ketones. The gram-scale preparation of aryl ketone through this strategy was easily achieved by using only 3 mol % of the iron catalyst. As a proof-of-concept, the bioactive molecule flurprimidol was synthesized in two steps by using this strategy.
Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation
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Paragraph 0049-0050, (2020/05/05)
The invention discloses a method for preparing an aryl ketone derivative based on a free radical-free radical cross-coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation. The method comprises the following steps: reacting aryl-substituted ketonic acid with fatty aldehyde under the catalytic action of ferric triacetylacetonate to generate an aryl ketone derivative; the gram-grade reaction can be realized by the method only by using 3mol% of an iron catalyst; and the method has the advantages of no need of consumption of a large amount of a Lewis acid catalyst or a stoichiometric organic metal reagent, mild reaction conditions, one-step reaction, few by-products, wide substrate application range and scalable reaction, and overcomes the defects of large catalyst consumption, insufficient functional group tolerance, many by-products and the like in the prior art.
One-Pot Conversion of Allylic Alcohols to α-Methyl Ketones via Iron-Catalyzed Isomerization-Methylation
Latham, Daniel E.,Polidano, Kurt,Williams, Jonathan M. J.,Morrill, Louis C.
supporting information, p. 7914 - 7918 (2019/10/16)
A one-pot iron-catalyzed conversion of allylic alcohols to α-methyl ketones has been developed. This isomerization-methylation strategy utilized a (cyclopentadienone)iron(0) carbonyl complex as precatalyst and methanol as the C1 source. A diverse range of allylic alcohols undergoes isomerization-methylation to form α-methyl ketones in good isolated yields (up to 84% isolated yield).
Silver-promoted cascade radical cyclization of γ,δ-unsaturated oxime esters with P(O)H compounds: synthesis of phosphorylated pyrrolines
Chen, Chen,Bao, Yinwei,Zhao, Jinghui,Zhu, Bolin
supporting information, p. 14697 - 14700 (2019/12/11)
A cascade radical cyclization was realized for the first silver-promoted imino-phosphorylation of γ,δ-unsaturated oxime esters, which provided a step-economical and redox-neutral route to access a variety of phosphorylated pyrrolines in good to excellent yields. Moreover, a new bulky trivalent phosphine ligand with a pyrroline motif was obtained through a deoxidation process.
α-Methylation of Ketones with Methanol Catalyzed by Ni/SiO2-Al2O3
Charvieux, Aubin,Duguet, Nicolas,Métay, Estelle
supporting information, p. 3694 - 3698 (2019/06/13)
α-Methylation of ketones with methanol catalyzed by a cheap and easy to handle Ni/SiO2-Al2O3 was explored. After optimization of the reaction between propiophenone and methanol, the desired product was obtained in 95 % isolated yield. A wide range of ketones was methylated under the optimized conditions (16 examples). This procedure was extended to a three-component cross-benzylation-methylation of acetophenone.
Catalytic C1 Alkylation with Methanol and Isotope-Labeled Methanol
Sklyaruk, Jan,Borghs, Jannik C.,El-Sepelgy, Osama,Rueping, Magnus
supporting information, p. 775 - 779 (2019/01/04)
A metal-catalyzed methylation process has been developed. By employing an air- and moisture-stable manganese catalyst together with isotopically labeled methanol, a series of D-, CD3-, and 13C-labeled products were obtained in good yields under mild reaction conditions with water as the only byproduct.
Rhodium-Catalyzed Direct Ortho C-H Arylation Using Ketone as Directing Group with Boron Reagent
Zhang, Bing,Wang, Huai-Wei,Kang, Yan-Shang,Zhang, Ping,Xu, Hua-Jin,Lu, Yi,Sun, Wei-Yin
supporting information, p. 5940 - 5943 (2017/11/10)
A general method for selective ortho C-H arylation of ketone, with boron reagent enabled by rhodium complexes with excellent yields, is developed. The transformation is characterized by the use of air-stable Rh catalyst, high monoarylation selectivity, and excellent yields of most of the substrates.
Methylation of C(sp3)-H/C(sp2)-H bonds with methanol catalyzed by cobalt system
Liu, Zhenghui,Yang, Zhenzhen,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
supporting information, p. 5228 - 5231 (2017/11/06)
A highly efficient Co-based catalytic system, composed of a commercially available Co salt, a tetradentate phosphine ligand P-(CH2CH2PPh2)3(PP3), and a base (denoted as [Co]/PP3/base), is developed for the methylation of C(sp3)-H and C(sp2)-H bonds using methanol as a methylating reagent. The Co(BF4)2.6H2O/PP3/K2CO3 catalytic system showed high catalytic activity for the methylation of C-H bonds in aryl alkyl ketones, aryl acetonitriles, and indoles, with wide substrate scope and good functional group tolerance, and methylsubstituted products were obtained in good to excellent yields at 100 °C. This cheap, readily available, and highly efficient Co-based catalytic system may have promising applications in methylation reaction using methanol.
