606-28-0Relevant articles and documents
Aromatization as an Impetus to Harness Ketones for Metallaphotoredox-Catalyzed Benzoylation/Benzylation of (Hetero)arenes
Chen, Ting-Wei,Cheng, Cheng-Ku,Chiu, Cheng-Chau,Huang, Pin-Gong,Lee, Shao-Chi,Lee, Yi-Hsin,Li, Li-Yun,Liao, Hsuan-Hung,Lin, Heng-Bo,Tsai, Zong-Nan,Tsao, Yong-Ting,Yang, Chung-Hsin
, (2022/01/04)
Herein we report ketones as feedstock materials in radical cross-coupling reactions under Ni/photoredox dual catalysis. In this approach, simple condensation first converts ketones into prearomatic intermediates that then act as activated radical sources for cross-coupling with aryl halides. Our strategy enables the direct benzylation/benzoylation of (hetero)arenes under mild reaction conditions with high functional group tolerance.
EFFICIENT AND SELECTIVE ROUTE FOR THE SYNTHESIS OF ALKYL 2-BENZOYLBENZOATE
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Paragraph 0028, (2021/08/27)
A method for preparing an alkyl 2-benzoylbenzoate comprising reacting a dialkyl phthalate with a Grignard reagent in the presence of an oxygenated solvent. The Grignard reagent may be selected from phenyl magnesium bromide, phenyl magnesium chloride, and phenyl magnesium iodide.
Acyl radicals from α-keto acids using a carbonyl photocatalyst: Photoredox-catalyzed synthesis of ketones
Zhu, Da-Liang,Wu, Qi,Young, David James,Wang, Hao,Ren, Zhi-Gang,Li, Hong-Xi
supporting information, p. 6832 - 6837 (2020/10/12)
Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridylstabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.
Palladium-Catalyzed Direct Oxidative Coupling of Iodoarenes with Primary Alcohols Leading to Ketones: Application to the Synthesis of Benzofuranones and Indenones
Suchand, Basuli,Sreenivasulu, Chinnabattigalla,Satyanarayana, Gedu
, p. 4832 - 4843 (2019/07/31)
In the present study, a palladium-catalyzed direct oxidative acylation through cross-dehydrogenative coupling has been investigated, utilizing readily available primary alcohols as acylating sources. Overall, this oxidative coupling proceeds via three distinct transformations such as oxidation, radical formation, and cross-coupling in one catalytic process. This protocol does not involve the assistance of a directing group or activation of the carbonyl group by any other means. Furthermore, this reaction made use of no toxic CO gas as carbonylating agent; instead, feedstock primary alcohols have been utilized as acylation source. Notably, the synthesis of benzofuranones and indenones is enabled. This strategy was also applied to the synthesis of n-butylphthalide, fenofibrate, pitofenone, and neo-lignan.
Metal-Free Arylation-Lactonization Sequence of γ-Alkenoic Acids Using Anilines as Aryl Radical Precursors
Felipe-Blanco, Diego,Gonzalez-Gomez, Jose C.
, p. 7735 - 7744 (2019/12/24)
The presence of salicylic acid (10 mol-%) and H2O (10 equiv.) significantly improves the arylation-lactonization sequence of γ-alkenoic acids with in situ formed diazonium salts (from bench stable anilines). The reaction is finished in less than 5 h without thermal or photochemical activation, giving access to a variety of γ,γ-disubstituted butyrolactones. The protocol is user-friendly and can be used at gram-scale or adapted to transform alkenols into phthalanes. Control experiments revealed that aryl radicals participate in the reaction and a plausible mechanism is proposed to include this and other mechanistic investigations, for the catalyzed and the background reaction.
Palladium-Catalyzed Acylation Reactions: A One-Pot Diversified Synthesis of Phthalazines, Phthalazinones and Benzoxazinones
Suchand, Basuli,Satyanarayana, Gedu
, p. 2233 - 2246 (2018/06/04)
A sequential one-pot strategy for the diversified synthesis of phthalazines, phthalazinones and benzoxazinones was presented. This strategy proceeds through [Pd]-catalyzed acylation and nucleophilic cyclocondensation with dinucleophilic reagents. This process was based on direct coupling with simple bench-top aldehydes without the assistance of directing group and without activating the carbonyl group. The process is highly advantageous because it employs simple nitrogen-based nucleophiles, and non-toxic and readily accessible aldehydes as the carbonyl source. Most importantly, the strategy was applied to the one-pot synthesis of PDE-4 inhibitor.
Ruthenium-Catalyzed Enantioselective Hydrogenation/Lactonization of 2-Acylarylcarboxylates: Direct Access to Chiral 3-Substituted Phthalides
Lu, Bin,Zhao, Mengmeng,Ding, Guangni,Xie, Xiaomin,Jiang, Lili,Ratovelomanana-Vidal, Virginie,Zhang, Zhaoguo
, p. 3989 - 3996 (2017/09/13)
Highly enantioselective tandem hydrogenation/lactonization of various 2-acylarylcarboxylates including 2-aroylarylcarboxylates were realized by using [RuCl(benzene)(S)-SunPhos]Cl as the catalyst under mild reaction conditions. Excellent enantioselectivities (up to 99.6 % ee) and activities (S/C=1000) were obtained. This convenient and practical method enables a direct access to a series of highly optically pure 3-substituted phthalides that are very important molecules as valuable pharmacological compounds and diversified synthons for medicinal chemistry. Moreover, a gram-scale reaction was performed to further demonstrate the practicality of this approach.
Preparation method of o-arylformacyl benzoate
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Paragraph 0013-0014, (2017/07/19)
The invention provides a preparation method of o-arylformacyl benzoate.3-alkoxyisobenzofuryl ketone compounds used as the raw material are subjected to rearrangement reaction under the protonic acid catalytic condition to obtain the o-arylformacyl benzoate.
Iodobenzene-Catalyzed Synthesis of Phenanthridinones via Oxidative C-H Amidation
Liang, Dongdong,Yu, Wenbo,Nguyen, Nam,Deschamps, Jeffrey R.,Imler, Gregory H.,Li, Yue,MacKerell, Alexander D.,Jiang, Chao,Xue, Fengtian
, p. 3589 - 3596 (2017/04/11)
We report a novel synthesis of phenanthridinones from N-methoxybenzamides using an oxidative C-H amidation reaction at room temperature in open air with modest to excellent yields. This method demonstrated unprecedented substrate scope. In particular, it solved the long-standing challenge in the synthesis of phenanthridinones with sterically demanding substitutions.
Palladium-Catalyzed Environmentally Benign Acylation
Suchand, Basuli,Satyanarayana, Gedu
, p. 6409 - 6423 (2016/08/16)
Recent trends in research have gained an orientation toward developing efficient strategies using innocuous reagents. The earlier reported transition-metal-catalyzed carbonylations involved either toxic carbon monoxide (CO) gas as carbonylating agent or functional-group-assisted ortho sp2 C-H activation (i.e., ortho acylation) or carbonylation by activation of the carbonyl group (i.e., via the formation of enamines). Contradicting these methods, here we describe an environmentally benign process, [Pd]-catalyzed direct carbonylation starting from simple and commercially available iodo arenes and aldehydes, for the synthesis of a wide variety of ketones. Moreover, this method comprises direct coupling of iodoarenes with aldehydes without activation of the carbonyl and also without directing group assistance. Significantly, the strategy was successfully applied to the synthesis n-butylphthalide and pitofenone.
