19969-04-1Relevant articles and documents
Ruthenium-on-Carbon-Catalyzed Facile Solvent-Free Oxidation of Alcohols: Efficient Progress under Solid-Solid (Liquid)-Gas Conditions
Park, Kwihwan,Jiang, Jing,Yamada, Tsuyoshi,Sajiki, Hironao
, p. 1200 - 1205 (2021/12/29)
A protocol for the ruthenium-on-carbon (Ru/C)-catalyzed solvent-free oxidation of alcohols, which proceeds efficiently under solid-solid (liquid)-gas conditions, was developed. Various primary and secondary alcohols were transformed to corresponding aldehydes and ketones in moderate to excellent isolated yields by simply stirring in the presence of 10% Ru/C under air or oxygen conditions. The solvent-free oxidation reactions proceeded efficiently regardless of the solid or liquid state of the substrates and reagents and could be applied to gram-scale synthesis without loss of the reaction efficiency. Furthermore, the catalytic activity of Ru/C was maintained after five reuse cycles.
Efficient Generation and Synthetic Applications of Alkyl-Substituted Siloxycarbenes: Suppression of Norrish-Type Fragmentations of Alkanoylsilanes by Triplet Energy Transfer
Abe, Manabu,Hagiwara, Chihiro,Ishida, Kento,Kusama, Hiroyuki,Yamazaki, Hokuto
supporting information, p. 1249 - 1253 (2020/02/04)
Acylsilanes have been known to undergo isomerization to siloxycarbenes under photoirradiation and the thus generated carbenes can be utilized for various synthetic reactions. But this carbene formation is not necessarily efficient with some alkanoylsilanes because Norrish-type fragmentations compete, which limit the synthetic utility of alkanoylsilanes as carbene precursors. In this study, generation of siloxycarbenes from alkanoylsilanes by visible-light-induced energy transfer was examined by using an Ir complex, [Ir{dF(CF3)ppy}2(dtbpy)]PF6, and was successfully applied to the C?C coupling reactions with boronic esters or aldehydes. This methodology efficiently suppressed undesired Norrish-type reactions and broadened synthetic utility of alkanoylsilanes.
Selective Ketone Formations via Cobalt-Catalyzed β-Alkylation of Secondary Alcohols with Primary Alcohols
Pandey, Bedraj,Xu, Shi,Ding, Keying
supporting information, p. 7420 - 7423 (2019/10/02)
A homogeneous cobalt-catalyzed β-alkylation of secondary alcohols with primary alcohols to selectively synthesize ketones via acceptorless dehydrogenative coupling is reported for the first time. Notably, this transformation is environmentally benign and atom economical with water and hydrogen gas as the only byproducts.
Synthetic method of aryl ketone compound
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Paragraph 0049-0053; 0059-0066; 0067-0076; 0077-0083-0104, (2017/08/25)
The invention relates to a synthetic method of an aryl ketone compound which can be used as a medicine intermediate and is as shown in the following formula (III) (as shown in the description). The method comprises the following steps of in an organic solvent, in the presence of a catalyst, an oxidizing agent, an organic ligand, alkali and an activator, enabling a compound in the following formula (I) and a compound in a formula (II) to be subjected to a reaction, after the reaction is finished, performing post-treatment so as to obtain the compound in the formula (III), (as shown in the description), wherein R1 is selected from H, C1-C6 alkyl or C1-C6 alkoxy, R2 is C1-C6 alkyl, and X is halogen. According to the method, a novel reaction material and a novel catalytic system are adopted, a plurality of characteristics are in comprehensive coordination, so that high-efficient preparation of the aryl ketone compound is realized, the sources of materials are developed, the yield of products is increased, and the method has broad industrial prospects.
Synthetic method of medical intermediate diaryl ketone compound
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Paragraph 0066; 0067; 0068; 0069; 0070, (2017/04/29)
The invention relates to a synthetic method of a diaryl ketone compound which can be used as a medical intermediate and is as shown in the formula (III). The method comprises the following steps: in an organic solvent and in the presence of a catalyst, an oxidizing agent, an organic ligand and alkali, a compound as shown in the formula (I) and a compound as shown in the formula (II) react; and after the reaction, the reaction product undergoes postprocessing so as to obtain the compound as shown in the formula (III). In the formula (III), R1 is selected from H, C1-C6 alkyl group or C1-C6 alkoxy group; R2 is selected from C1-C6 alkyl group or unsubstituted or phenyl group bearing substituent group, wherein the substituent group is C1-C6 alkyl group or halogen; and X is halogen. According to the method, novel reaction materials and catalytic system are adopted. Through integrated collaboration of multiple characteristics, efficient preparation of the diaryl ketone compound is realized. Sources of materials are widened, and yield of the product is raised. The synthetic method has a wide industrial prospect.
A general method for the direct transformation of common tertiary amides into ketones and amines by addition of Grignard reagents
Huang, Pei-Qiang,Wang, Yu,Xiao, Kai-Jiong,Huang, Ying-Hong
, p. 4248 - 4254 (2015/06/02)
The direct transformation of amides into ketones by addition of organometallic reagents has attracted the attention of organic chemists for a long time. However limited methods are reliable for common amides and have found synthetic applications. Here we report a method featuring in situ activation of tertiary amides with triflic anhydride (Tf2O) followed by addition of Grignard reagents. The method displays a good generality in scope for both amides and Grignard reagents, and it can be viewed as the acylation of Grignard reagents using amides as stable and selective acylating agents. Moreover, this deaminative alkylation reaction provides a mild method for the N-Deacylation of amides to give free amines.
Continuous flow synthesis of ketones from carbon dioxide and organolithium or grignard reagents
Wu, Jie,Yang, Xiaoqing,He, Zhi,Mao, Xianwen,Hatton, T. Alan,Jamison, Timothy F.
supporting information, p. 8416 - 8420 (2014/08/18)
We describe an efficient continuous flow synthesis of ketones from CO 2 and organolithium or Grignard reagents that exhibits significant advantages over conventional batch conditions in suppressing undesired symmetric ketone and tertiary alcohol byproducts. We observed an unprecedented solvent-dependence of the organolithium reactivity, the key factor in governing selectivity during the flow process. A facile, telescoped three-step-one-flow process for the preparation of ketones in a modular fashion through the in-line generation of organometallic reagents is also established.
Deaminative and decarboxylative catalytic alkylation of amino acids with ketones
Kalutharage, Nishantha,Yi, Chae S.
supporting information, p. 13651 - 13655 (2014/01/06)
It cuts two ways: The cationic [Ru-H] complex catalyzes selective coupling of α- and β-amino acids with ketones to form α-alkylated ketone products. The reaction involves C-C and C-N bond cleavage which result in regio- and stereoselective alkylation using amino acids. A broad substrate scope and high functional-group tolerance is demonstrated. Copyright
Photochemically promoted transition metal-free cross-coupling of acylsilanes with organoboronic esters
Ito, Kazuta,Tamashima, Hiroto,Iwasawa, Nobuharu,Kusama, Hiroyuki
supporting information; experimental part, p. 3716 - 3719 (2011/05/14)
Intermolecular carbon-carbon bond formation between acylsilanes and organoboronic esters was achieved by photoirradiation under almost neutral, transition metal-free conditions. In this reaction, siloxycarbenes generated by photoisomerization of acylsilanes reacted with boronic esters to give the formal B-C bond insertion intermediates, which underwent unique rearrangement to afford the cyclic α-alkoxyboronic esters. Acidic treatment of the resulting crude products under air furnished the cross-coupled ketones in good yields.
Cyanocuprates convert carboxylic acids directly into ketones
Genna, Douglas T.,Posner, Gary H.
supporting information; experimental part, p. 5358 - 5361 (2011/12/15)
Carboxylic acids were converted directly in 56-99% yields into methyl, n-butyl, and isopropyl ketones using excess cyanocuprates R2CuLi 3 LiCN. A substrate with a stereocenter α to the carboxylic acid was converted into ketones with very little loss of enantiomeric purity. A variety of functional groups were tolerated including aryl bromides. This direct transformation of a carboxylic acid into ketone with minimal tertiary alcohol formation is proposed to involve a relatively stable copper ketal tetrahedral intermediate.
