- Rhodium-Catalyzed Deoxygenation and Borylation of Ketones: A Combined Experimental and Theoretical Investigation
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The rhodium-catalyzed deoxygenation and borylation of ketones with B2pin2 have been developed, leading to efficient formation of alkenes, vinylboronates, and vinyldiboronates. These reactions feature mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes via boron enolate intermediates, and the subsequent Rh-catalyzed dehydrogenative borylation of alkenes leads to the formation of vinylboronates and diboration products, which is also supported by density functional theory calculations.
- Tao, Lei,Guo, Xueying,Li, Jie,Li, Ruoling,Lin, Zhenyang,Zhao, Wanxiang
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supporting information
p. 18118 - 18127
(2020/11/26)
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- Efficient Organoruthenium Catalysts for α-Alkylation of Ketones and Amide with Alcohols: Synthesis of Quinolines via Hydrogen Borrowing Strategy and their Mechanistic Studies
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A new family of phosphine free organometallic ruthenium(II) catalysts (Ru1–Ru4) supported by bidentate NN Schiff base ligands (L1–L4 where L1=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl) aniline, L2=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-ylmethyl)hydrazineylidene)methyl)aniline, L3=N,N-dimethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl)- aniline and L4=N,N-diethyl-4-((2-phenyl-2-(pyridin-2-yl)hydrazineylidene)methyl) aniline) was prepared and characterized. These half-sandwich complexes acted as catalysts for C?C bond formation and exhibited excellent performance in the dehydrogenative coupling of ketones and amides. In the synthesis of C–C bonds, alcohols were utilized as the alkylating agent. A broad range of substrates, including sterically hindered ketones and alcohols, were well tolerated under the optimized conditions (TON up to 47000 and TOF up to 11750 h?1). This ruthenium (II) catalysts were also active towards the dehydrogenative cyclization of o-amino benzyl alcohol for the formation of quinolines derivatives. Various polysubstituted quinolines were synthesized in moderate to excellent yields (TON up to 71000 and TOF up to 11830 h?1). Control experiments were carried out and the ruthenium hydride intermediate was characterized to support the reaction mechanism and a probable reaction pathway of dehydrogenative coupling for the C?C bond formation has been proposed.
- Maji, Ankur,Singh, Anshu,Singh, Neetu,Ghosh, Kaushik
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p. 3108 - 3125
(2020/05/18)
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- Suzuki-Miyaura coupling of simple ketones via activation of unstrained carbon-carbon bonds
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Here, we describe that simple ketones can be efficiently employed as electrophiles in Suzuki-Miyaura coupling reactions via catalytic activation of unstrained C-C bonds. A range of common ketones, such as cyclopentanones, acetophenones, acetone and 1-indanones, could be directly coupled with various arylboronates in high site-selectivity, which offers a distinct entry to more functionalized aromatic ketones. Preliminary mechanistic study suggests that the ketone α-C-C bond was cleaved via oxidative addition.
- Xia, Ying,Wang, Jianchun,Dong, Guangbin
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supporting information
p. 5347 - 5351
(2018/05/03)
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- Co (II)-C12 alkyl carbon chain multi-functional ionic liquid immobilized on nano-SiO2 nano-SiO2@CoCl3-C12IL as an efficient cooperative catalyst for C–H activation by direct acylation of aryl halides with aldehydes
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Nano-silica supported ionic liquids composed of alkyl carbon chain and transition metal chlorides anions have been prepared and successfully applied as a heterogeneous catalyst in the direct aldehyde C-H activation. Catalytic results indicated that nano-SiO2 supported ionic liquid consisting C12 alkyl carbon chain and CoCl3 anion nano-SiO2@CoCl3-C12IL showed excellent catalytic properties with good to excellent yields towards the desired aryl ketones. The excellent recyclability of the supported catalyst, mild reaction conditions, low catalyst loading, and operational simplicity are the important features of this methodology.
- Hu, Yu Lin,Wu, Ya Pan,Lu, Ming
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- P -Selective (sp2)-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis
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p-Selective (sp2)-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.
- Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana,Vanka, Kumar,Jain, Shailja
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p. 12337 - 12340
(2017/11/20)
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- One-pot sequential 1,2-addition, Pd-catalysed cross-coupling of organolithium reagents with Weinreb amides
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An efficient sequential 1,2-addition/cross-coupling of Weinreb amides with two organolithium reagents is reported. This synthetic approach allows access to a wide variety of functionalized ketones in a modular way. The one-pot procedure presented here takes advantage of a kinetically stable tetrahedral Weinreb intermediate during subsequent Pd-catalyzed cross-coupling with the second organolithium reagent leading, within short reaction times and under mild conditions, to the formation of ketones in excellent overall yields.
- Giannerini,Vila,Hornillos,Feringa
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supporting information
p. 1206 - 1209
(2016/01/15)
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- Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
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Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
- Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
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p. 4420 - 4424
(2014/06/10)
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- A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
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The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
- Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
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p. 1011 - 1019
(2013/05/09)
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- An effective one-pot conversion of acid chlorides to aldehydes and ketones
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Aldehydes and ketones were synthesized from their respective acid chlorides via a one-pot protocol. Morpholine amide intermediates that were readily prepared by the aminolysis of various acid chlorides with diisobutyl(morpholino) aluminum smoothly reacted with the reducing agent LDBMA and the organolithium reagents under mild reaction conditions (0 C), giving almost excellent product yields of up to 95%.
- Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
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p. 3199 - 3203
(2013/06/27)
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- A remarkable effect of ionic liquids in transition-metal-free aerobic oxidation of benzylic alcohols
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The transition-metal-free aerobic oxidation of benzylic alcohols is uniquely accelerated by a 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6)/PhCF3 biphasic system and Cs2CO 3 to afford the corresponding ketones in good yields. The reaction system is also applicable to an oxidative cross-esterification of primary benzyl alcohols with a higher aliphatic alcohol.
- Oda, Yoshiro,Hirano, Koji,Satoh, Tetsuya,Kuwabata, Susumu,Miura, Masahiro
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supporting information; experimental part
p. 5392 - 5394
(2011/10/19)
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- Direct synthesis of aryl ketones by palladium-catalyzed desulfinative addition of sodium sulfinates to nitriles
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Mild yet direct: A convenient and efficient method for the synthesis of various aryl ketones by palladium-catalyzed desulfinative addition of aromatic sulfinic acid sodium salts to various nitriles is described (see scheme). Aromatic and aliphatic nitriles are successfully reacted with arenesulfinic acid sodium salts to form aryl ketones in good yields.
- Liu, Jing,Zhou, Xianya,Rao, Honghua,Xiao, Fuhong,Li, Chao-Jun,Deng, Guo-Jun
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supporting information; experimental part
p. 7996 - 7999
(2011/08/22)
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- Reactivities of mixed organozinc and mixed organocopper reagents, 2. Selective n-alkyl transfer in tri-n-butylphosphine-catalyzed acylation of n-alkyl phenylzincs; an atom economic synthesis of n-alkyl aryl ketones
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Tri-n-butylphosphine-catalyzed acylation of mixed n-alkyl phenylzincs with aromatic acyl halides in THF is efficient in selective transfer of n-alkyl groups to produce n-alkyl aryl ketones in good yields. This route provides an atom economic organocatalyzed alternative to transition metal-catalyzed acylation of di-n-alkylzincs.
- Erdik, Ender,Pekel, ?zgen ?mür
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experimental part
p. 1501 - 1503
(2009/06/21)
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- One-step preparation of α-chlorostyrenes
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α-Chlorostyrenes were prepared via a one-step method involving Friedel-Crafts reaction of various aromatic substrates with acid chlorides in the presence of a heterogeneous Si-Fe catalyst.
- Borate, Hanumant B.,Gaikwad, Abaji G.,Maujan, Suleman R.,Sawargave, Sangmeshwer P.,Kalal, Kamalakar M.
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p. 4869 - 4872
(2008/02/05)
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- 1-(4-Methylphenyl)-2-pyrrolidin-1-yl-pentan-1-one (pyrovalerone) analogues: A promising class of monoamine uptake inhibitors
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Dopamine, serotonin, and norepinephrine are essential for neurotransmission in the mammalian system. These three neurotransmitters have been the focus of considerable research because the modulation of their production and their interaction at monoamine receptors has profound effects upon a multitude of pharmacological outcomes. Our interest has focused on neurotransmitter reuptake mechanisms in a search for medications for cocaine abuse. Herein we describe the synthesis and biological evaluation of an array of 2-aminopentanophenones. This array has yielded selective inhibitors of the dopamine and norepinephrine transporters with little effect upon serotonin trafficking. A subset of compounds had no significant affinity at 5HT1A, 5HT1B, 5HT1C, D1, D2, or D3 receptors. The lead compound, racemic 1-(4-methylphenyl)-2-pyrrolidin-1-yl-pentan-1-one 4a, was resolved into its enantiomers and the S isomer was found to be the most biologically active enantiomer. Among the most potent of these DAT/NET selective compounds are the 1-(3,4-dichlorophenyl)- (4u) and the 1-naphthyl- (4t) 2-pyrrolidin-1-yl-pentan-1-one analogues.
- Meltzer, Peter C.,Butler, David,Deschamps, Jeffrey R.,Madras, Bertha K.
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p. 1420 - 1432
(2007/10/03)
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- Palladium-catalyzed coupling of thiol esters with aryl and primary and secondary alkyl organoindium reagents
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Thiol esters and organoindium reagents undergo palladium-catalyzed cross-coupling under mild conditions to give ketones in moderate to excellent yields. Aryl and primary/ secondary alkyl organoindium reagents can be used as coupling partners. This method has two advantages over the cross-coupling of thiol esters with boron and tin reagents: (1) no added copper reagent is required to mediate the reaction and (2) for the case of alkyl transfer, no added base is required to activate organoindium reagents for cross-coupling as is required for the coupling of alkyl boron reagents with thiol esters.
- Fausett, Bryan W.,Liebeskind, Lanny S.
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p. 4851 - 4853
(2007/10/03)
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- Highly efficient Pd-catalyzed carbonylative cross-coupling reactions with tetraorganoindates
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Tetraorganoindates, which were prepared easily from the reaction of 1 equiv of InCl3 with 4 equiv of organometallics, could be employed as effective nucleophilic cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method gave unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under a carbon monoxide atmosphere in THF at 60 °C.
- Lee, Sung Wook,Lee, Kooyeon,Seomoon, Dong,Kim, Sundae,Kim, Hyunseok,Kim, Hyun,Shim, Eunkyong,Lee, Miae,Lee, Seokju,Kim, Misook,Lee, Phil Ho
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p. 4852 - 4855
(2007/10/03)
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- The Dual Roles of Oxodiperoxovanadate Both as a Nucleophile and an Oxidant in the Green Oxidation of Benzyl Alcohols or Benzyl Halides to Aldehydes and Ketones
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One catalyst, two roles: VO(O2)2- reacts as a nucleophilic oxidant under acidic conditions towards benzyl alcohols. Altogether 15 alcohols have been oxidized, in the absence of organic solvent, in excellent yields. Benzyl halides are also oxidized by H2O 2 in water catalyzed by oxodiperoxovanadate and a phase transfer catalyst into aromatic aldehydes and ketones (see scheme). This reaction is the first green oxidation of benzyl halides.
- Li, Chunbao,Zheng, Pengwu,Li, Jie,Zhang, Hang,Cui, Yi,Shao, Qiyun,Ji, Xiujie,Zhang, Jian,Zhao, Pengying,Xu, Yanli
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p. 5063 - 5066
(2007/10/03)
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- Pd-catalyzed carbonylative cross-coupling reactions by triorganoindiums: Highly efficient transfer of organic groups attached to indium under atmospheric pressure
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(Matrix presented) A highly atom-efficient synthetic method of unsymmetrical ketones was developed by using trialkyl- and triarylindiums, which could be employed as effective cross-coupling partners in Pd-catalyzed carbonylative cross-coupling reactions with a variety of organic electrophiles. The present method produced unsymmetrical ketones and 1,4-diacylbenzenes in good yields with highly efficient transfer of almost all the organic groups attached to the indium under atmospheric pressure of CO gas in THF at 66°C.
- Lee, Phil Ho,Lee, Sung Wook,Lee, Kooyeon
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p. 1103 - 1106
(2007/10/03)
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- Palladium-catalyzed carbonylative coupling reactions using triorganoindium compounds
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A novel palladium-catalyzed carbonylative cross-coupling reaction that employs triorganoindium compounds is described. The reaction proceeds under a carbon monoxide atmosphere with alkyl-, alkynyl-, and arylindium reagents to give good yields of unsymmetrical ketones with high atom economy. All three organic groups attached to the metal are efficiently transferred in this carbonylative coupling reaction.
- Pena, Miguel A.,Perez Sestelo, Jose,Sarandeses, Luis A.
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p. 780 - 784
(2007/10/03)
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- THE VINYLATION OF ARENES WITH 1-(PHENYLTHIO)VINYLSTANNANES
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The vinylation of arenes using 1-(phenylthio)vinylstannanes proceeded in the presence of tin(IV) chloride and molecular sieves 4A to afford 1-arylalkenyl sulfides in good yields.The stereochemistry of the olefinic moiety was determined after oxidation to the corresponding sulfones and it was found that the present reaction gave the thermodynamically stable stereoisomers.
- Takeda, Takeshi,Kanamori, Fumio,Masuda, Mitsutoshi,Fujiwara, Tooru
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p. 5567 - 5570
(2007/10/02)
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- The Direct Formation of Functionalized Alkyl(aryl)zinc Halides by Oxidative Addition of Highly Reactive Zinc with Organic Halides and Their Reactions with Acid Chlorides, α,β-Unsaturated Ketones, and Allylic, Aryl, and Vinyl Halides
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Highly reactive zinc, prepared by the lithium naphthalenide reduction of ZnCl2, readily undergoes oxidative addition to alkyl, aryl, and vinyl halides under mild conditions to generate the corresponding organozinc compounds in excellent yields.Significantly, the reaction will tolerate a spectrum of functional groups on the organic halides.Accordingly, this approach can now be used to prepare a wide variety of highly functionalized organozinc compounds.In the presence of Cu(I) salts, the organozinc compounds cross-couple with acid chlorides, conjugatively add to α,β-unsaturated ketones, and regioselectively undergo SN2' substitution reactions with allylic halides.They also cross-couple with aryl or vinyl halides with Pd(0) catalysts.
- Zhu, Lishan,Wehmeyer, Richard M.,Rieke, Reuben D.
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p. 1445 - 1453
(2007/10/02)
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- SELECTIVE CARBOPHILIC ADDITION OF ORGANOLITHIUMS TO THIOAMIDES. A NOVEL SYNTHESIS OF UNSYMMETRICAL KETONES AND α-ALKYLATED AMINES
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Thioamides, readily available from aldehydes, sulfur and secondary amines, can be converted to unsymmetrical ketones by the carbophilic addition of organolithiums to the thiocarbonyl group.Reduction of the intermediates with lithium aluminium hydride gives α-alkylated or α-arylated amines.
- Tominaga, Yoshinori,Kohra, Shinya,Hosomi, Akira
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p. 1529 - 1532
(2007/10/02)
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- The Chemistry of N-Substituted Benzotriazoles. Part 6. A New Synthetic Route to Aromatic Ketones
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Lithiation of p-bis(benzotriazol-1-yl)methyltoluene (4) gives the carbanion (5) which affords substitution products with many electrophiles.Acidic hydrolysis of the lithiation products affords the corresponding aromatic ketones in good yield.The syntheses of simple ketones, of diketones, and of α-hydroxy ketones are described.
- Katritzky, Alan R.,Kuzmierkiewicz, Wojciech
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p. 819 - 824
(2007/10/02)
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