4842-45-9Relevant academic research and scientific papers
Iodide-Catalyzed Carbonylation-Benzylation of Benzyl Chlorides with Potassium Aryltrifluoroborates under Ambient Pressure of Carbon Monoxide
Han, Wei,Chen, Junjie,Jin, Fengli,Yuan, Xiaorong
, p. 369 - 374 (2018)
Tetra- N -butylammonium iodide (TBAI) catalyzed carbonylation-benzylation of unactivated benzyl chlorides with potassium aryltrifluoroborates using CO gas has been developed. This reaction is transition-metal free, is carried out under ambient pressure, and provides a wide range of 1,2,3-triarylpropan-1-one derivatives in high yields. The novel method represents a significant improvement over the traditional palladium-catalyzed carbonylation.
Transition-metal-free and base promoted C-C bond formationviaC-N bond cleavage of organoammonium salts
Chen, Tieqiao,Huang, Tianzeng,Ke, Yuting,Li, Chunya,Liu, Long,Tang, Yuanyuan,Tang, Zhi,Wang, Kunyu,Zhang, Tao
supporting information, p. 8237 - 8240 (2021/10/12)
A transition-metal-free and base promoted C-C bond forming reaction of benzyl C(sp3)-H bond with organoammonium saltsviaC-N bond cleavage has been reported. Benzyl ammonium salts as well as cinnamyl ammonium salt could couple readily with various benzyl C(sp3)-H species, producing the corresponding products in moderate to excellent yields with good functional group tolerance. Late stage chemical manipulation enabled the specific 1,2-diarylethane structure of products transformed into useful olefin compoundsviadehydrogenation, which further demonstrated the utility of this reaction.
Benzylic aroylation of toluenes with unactivated tertiary benzamides promoted by directed ortho-lithiation
Bao, Can-Can,Luo, Yan-Long,Du, Hui-Zhen,Guan, Bing-Tao
, p. 1349 - 1354 (2021/07/12)
The deprotonative functionalization of toluenes, for their weak acidity, generally needs strong bases, thus leading to the requirement of harsh conditions and the generation of by-products. Direct nucleophilic acyl substitution reaction of amides with organometallic reagents could provide an ideal solution for ketone synthesis. However, the inert amides and highly reactive organometallic reagents bring great challenges for an efficient and selective synthetic approach. Herein, we reported an lithium diisopropylamide (LDA)-promoted benzylic aroylation of toluenes with unactivated tertiary benzamides, providing a direct and efficient synthesis of various aryl benzyl ketones. This process features a kinetic deprotonative functionalization of toluenes with a readily available base LDA. Mechanism studies revealed that the directed ortho-lithiation of the tertiary benzamide with LDA promoted the benzylic kinetic deprotonation of toluene and triggered the nucleophilic acyl substitution reaction with the amide. [Figure not available: see fulltext.].
Visible-Light-Promoted Photocatalyst-Free Hydroacylation and Diacylation of Alkenes Tuned by NiCl2·DME
Zhao, Xinxin,Li, Bing,Xia, Wujiong
, p. 1056 - 1061 (2020/02/15)
Herein, we describe a visible light-promoted hydroacylation strategy that facilitates the preparation of ketones from alkenes and 4-acyl-1,4-dihydropyridines via an acyl radical addition and hydrogen atom transfer pathway under photocatalyst-free conditions. The efficiency was highlighted by wide substrate scope, good to high yields, successful scale-up experiments, and expedient preparation of highly functionalized ketone derivatives. In addition, this protocol allows for the synthesis of 1,4-dicarbonyl compounds through alkene diacylation in the presence of NiCl2·DME.
Iron-Catalyzed Ligand Free α-Alkylation of Methylene Ketones and β-Alkylation of Secondary Alcohols Using Primary Alcohols
Alanthadka, Anitha,Bera, Sourajit,Banerjee, Debasis
, p. 11676 - 11686 (2019/10/02)
Herein, we demonstrate a general and broadly applicable catalytic cross coupling of methylene ketones and secondary alcohols with a series of primary alcohols to disubstituted branched ketones. A simple and nonprecious Fe2(CO)9 catalyst enables one-pot oxidations of both primary and secondary alcohols to a range of branched gem-bis(alkyl) ketones. A number of bond activations and formations selectively occurred in one pot to provide the ketone products. Coupling reactions can be performed in gram scale and successfully applied in the synthesis of an Alzehimer's drug. Alkylation of a steroid hormone can be achieved. A single catalyst enables sequential one-pot double alkylation to bis-hetero aryl ketones using two different alcohols. Preliminary mechanistic studies using an IR probe, deuterium labeling, and kinetic experiments established the participation of a borrowing-hydrogen process using Fe catalyst, and the reaction produces H2 and H2O as byproducts.
Palladium on carbon-catalyzed Α-alkylation of ketones with alcohols as electrophiles: Scope and mechanism
Bennedsen, Niklas R.,Mortensen, Rasmus L.,Kramer, S?ren,Kegn?s, S?ren
, p. 153 - 160 (2019/02/14)
The α-alkylation of ketones with alcohols represents a green strategy for the formation of crucial carbon–carbon bonds since it only produces water as byproduct. In terms of reaction mechanism, the evidence for homogeneous catalysis supports a catalytic hydrogen-borrowing pathway; however, the reaction mechanism has not been investigated for heterogeneous Pd/C catalysts. Here, we report an improved method for α-alkylation of ketones with alcohols using commercially available Pd/C, ubiquitous in organic synthesis labs, as catalyst. The reaction conditions are mild compared to state-of-the-art for both homo- and heterogeneous catalysts, and the developed conditions produces quantitative yields for most ketones and alcohols. A hot filtration experiment and recycling of the catalyst supports the heterogeneous nature of catalysis. Importantly, the reaction mechanism is studied for the first time by a combination of stoichiometric experiments and kinetic analyses by in-situ IR (React-IR).
NNN pincer Ru(II)-complex-catalyzed α-alkylation of ketones with alcohols
Cao, Xiao-Niu,Wan, Xiao-Min,Yang, Fa-Liu,Li, Ke,Hao, Xin-Qi,Shao, Tian,Zhu, Xinju,Song, Mao-Ping
, p. 3657 - 3668 (2018/04/14)
A series of novel ruthenium(II) complexes supported by a symmetrical NNN ligand were prepared and fully characterized. These complexes exhibited good performance in transfer hydrogenation to form new C-C bonds using alcohols as the alkylating agents, generating water as the only byproduct. A broad range of substrates, including (hetero)aryl- or alkyl-ketones and alcohols, were well tolerated under the optimized conditions. Notably, α-substituted methylene ketones were also investigated, which afforded α-branched steric hindrance products. A potential application of α-alkylation of methylene acetone to synthesize donepezil was demonstrated, which provided the desired product in 83% yield. Finally, this catalytic system could be applied to a one-pot double alkylation procedure with sequential addition of two different alcohols. The current protocol is featured with several characteristics, including a broad substrate scope, low catalyst (0.50 mol %) loadings, and environmental benignity.
Mn(ii)-catalysed alkylation of methylene ketones with alcohols: Direct access to functionalised branched products
Kabadwal, Lalit Mohan,Das, Jagadish,Banerjee, Debasis
supporting information, p. 14069 - 14072 (2019/01/03)
Herein an operationally simple alkylation of methylene ketones with primary alcohols is reported. Use of an inexpensive and earth abundant Mn/1,10-phenanthroline system enables direct access to a series of functionalised branched ketones including one-pot sequential double alkylation and Alzheimer's drug donepezil. Preliminary mechanistic investigation, determination of the rate and order of reactions and deuterium labeling experiments support the participation of the hydrogen-borrowing strategy for the ketone alkylation.
Nickel-Catalyzed Hydrogen-Borrowing Strategy for α-Alkylation of Ketones with Alcohols: A New Route to Branched gem-Bis(alkyl) Ketones
Das, Jagadish,Singh, Khushboo,Vellakkaran, Mari,Banerjee, Debasis
, p. 5587 - 5591 (2018/09/25)
The α-alkylation of ketones using an earth-abundant and nonprecious NiBr2/L1 system is reported. This nickel-catalyzed reaction could be performed in gram scale and successfully applied in the synthesis of donepezil (Alzheimer's drug) and functionalization of steroid hormones and fatty acid derivatives. Synthesis of N-heterocycles, methylation of ketones, and one-pot double alkylation to bis-hetero aryl ketones using two different alcohols with a single catalyst broadens the scope of the catalytic protocol. Preliminary mechanistic studies using defined Ni-H species and deuterium-labeling experiments established the participation of the borrowing-hydrogen strategy.
Synthetic method for 1,2,3-triphenylpropan-1-one
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Paragraph 0016; 0017, (2018/05/01)
The invention discloses a method for synthesizing 1,2,3-triphenylpropan-1-one. The method comprises the following steps: adding phenylacetophenone, benzyl alcohol, a catalyst, an alkaline and a solvent into a reactor in sequence; performing magnetic stirring and reacting in an argon atmosphere; fully reacting in an oil bath pan; after the reaction is ended, performing vacuum rotating evaporation,chromatography separation and drying to obtain a target product. According to the method, the problem of a large amount of by-products caused by using reagents in a conventional synthesizing method isavoided, because the reagents are cheap, easy to store and environmentally friendly, and are renewable alternative petroleum base compounds. In the method, a NNN-type pincerlike metal ruthenium (II)compound is adopted as a catalyst of a catalytic reaction; the reaction is completed by one step; the operation is simple and convenient; the reaction efficiency is high; the requirement on sustainable development of green chemistry is met.
