- Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols
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An iron-catalyzed deconstruction/hydrogenation reaction of alcohols through C-C bond cleavage is developed through photocatalysis, to produce ketones or aldehydes as the products. Tertiary, secondary, and primary alcohols bearing a wide range of substituents are suitable substrates. Complex natural alcohols can also perform the transformation selectively. A investigation of the mechanism reveals a procedure that involves chlorine radical improved O-H homolysis, with the assistance of 2,4,6-collidine.
- Liu, Wei,Wu, Qiang,Wang, Miao,Huang, Yahao,Hu, Peng
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supporting information
p. 8413 - 8418
(2021/11/01)
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- Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
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Conversion of a wide range of N-Boc amides to aryl ketones was achieved with Grignard reagents via chemoselective C(O)-N bond cleavage. The reactions proceeded under catalyst-free conditions with different aryl, alkyl, and alkynyl Grignard reagents. α-Ketoamide was successfully converted to aryl diketones, while α,β-unsaturated amide underwent 1,4-addition followed by C(O)-N bond cleavage to provide diaryl propiophenones. N-Boc amides displayed higher reactivity than Weinreb amides with Grignard reagents. A broad substrate scope, excellent yields, and quick conversion are important features of this methodology.
- Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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p. 11823 - 11838
(2019/10/02)
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- Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedl?nder Quinoline Synthesis
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Herein, we report a very simple and inexpensive catalytic system based on Earth's abundant transition metal manganese and on a bench-stable phosphine-free NNN-pincer ligand for an atom-efficient α-alkylations of ketones with primary alcohols via hydrogen-autotransfer C?C bond formation protocol. The precatalyst could be generated in situ and could be activated by using catalytic amount of base under milder conditions. A range of ketones were efficiently diversified with a broad range of primary alcohols in good to excellent isolated yields. Remarkably, this catalyst could also be employed for the synthesis of quinoline derivatives using 2-aminobenzyl alcohol as an alkylating agent. The later reaction is highly benign producing only hydrogen and water as byproducts. (Figure presented.).
- Barman, Milan K.,Jana, Akash,Maji, Biplab
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supporting information
p. 3233 - 3238
(2018/07/31)
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- Syntheses, structures, and catalytic activity in Friedel–Crafts acylations of substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes
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Reactions of the substituted tetramethylcyclopentadienes [C5HMe4R] [R?=?tBu, Ph, CH2CH2C(CH3)3] with Mo(CO)3(CH3CN)3 in refluxing xylene gave a series of dinuclear molybdenum carbonyl complexes [(η5-C5Me4R)Mo(CO)3]2 [R?=?tBu (1), Ph (2), CH2CH2C(CH3)3 (3)], [(η5-C5MetBu)Mo(μ-CO)2]2 (4)], and [(η5-C5Me4)tBu]2Mo2O4(μ-O) (5)], respectively. Complexes 1–5 were characterized by elemental analysis, IR, 1H NMR, and 13C NMR spectroscopy. In addition, their crystal structures were determined by X-ray crystal diffraction analysis. The catalytic activities of complexes 1–3 in Friedel–Crafts acylation in the presence of o-chloranil has also been investigated; the reactions were achieved under mild conditions to give the corresponding products in moderate yields.
- Li, Tong,Yan, Xin-Long,Li, Zhan-Wei,Ma, Zhi-Hong,Li, Su-Zhen,Han, Zhan-Gang,Zheng, Xue-Zhong,Lin, Jin
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p. 313 - 322
(2018/02/22)
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- RhCl(CO)(PPh3)2 catalyzed α-alkylation of ketones with alcohols
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A simple and efficient method for α-alkylation of ketones with primary alcohols catalyzed by RhCl(CO)(PPh3)2 without additional additives under mild conditions is developed. It has a wide substrate scope, high atom-efficiency and chemoselectivity. It is an environmentally friendly method to build C[sbnd]C bond because water is the only byproduct.
- Wang, Rui,Huang, Lina,Du, Zhengyin,Feng, Hua
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supporting information
p. 40 - 43
(2017/06/07)
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- Acyl hydrazides as acyl donors for the synthesis of diaryl and aryl alkyl ketones
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In this communication we describe a novel strategy for the formation of valuable diaryl and aryl alkyl ketones from acyl hydrazides. A wide variety of ketones are prepared and the mild reaction conditions allow for the use of a range of functionalities, especially in the synthesis of diaryl ketones.
- Akhbar, Ahmed R.,Chudasama, Vijay,Fitzmaurice, Richard J.,Powell, Lyn,Caddick, Stephen
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p. 743 - 746
(2014/01/06)
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- Direct α-alkylation of ketones with alcohols in water
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The direct α-alkylation of ketones with alcohols has emerged as a new green protocol to construct C-C bonds with H2O as the sole byproduct. In this work, a very simple and convenient Pd/C catalytic system for the direct a-alkylation of ketones with primary alcohols in pure water is developed. Based on this catalytic system, aqueous mixtures of dilute acetone, 1-butanol, and ethanol (mimicking ABE fermentation products) can be directly transformed into C5-C11 or longer-chain ketones and alcohols, which are precursors to fuels.
- Xu, Guoqiang,Li, Qiong,Feng, Jiange,Liu, Qiang,Zhang, Zuojun,Wang, Xicheng,Zhang, Xiaoyun,Mu, Xindong
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p. 105 - 109
(2014/03/21)
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- An Efficient α-alkylation of aromatic ketones with primary alcohols catalyzed by [cp*ircl2]2 without solvent
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Aromatic ketones are directly alkylated at α position with primary alcohols at 110°C in the presence of catalytic amount of KOH and [Cp*IrCl2]2 (Cp=pentamethylcyclopentadienyl) catalyst. The reaction is carried out in the absence of any solvent or additive, which generates only water as the byproduct in theory. It is very efficient and generally completed in 10 min in good isolated yields. The reaction is believed to undergo successive hydrogen transfer and cross aldol condensation processes. Copyright
- Li, Jian,Zhang, Weixing,Wang, Feng,Jiang, Min,Dong, Xiaochun,Zhao, Weili
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p. 2363 - 2366,4
(2020/09/16)
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- Direct acylation of aryl bromides with aldehydes by palladium catalysis
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A new protocol for the direct acylation of aryl bromides with aldehydes is established. It appears to involve palladium-amine cooperative catalysis, affording synthetically important alkyl aryl ketones in moderate to excellent yields in a straightforward manner, and broadening the scope of metal-catalyzed coupling reactions. Copyright
- Ruan, Jiwu,Saidi, Ourida,Iggo, Jonathan A.,Xiao, Jianliang
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supporting information; experimental part
p. 10510 - 10511
(2009/02/05)
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- Ir- and Ru-catalyzed sequential reactions: Asymmetric α-alkylative reduction of ketones with alcohols
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(Chemical Equation Presented) The compatibility between [{IrCl(cod)} 2] and ruthenium complex 1 to achieve asymmetric α-alkylative reduction of prochiral ketones with primary alcohols is an essential factor in obtaining optically active alcohols with elongation of the carbon skeleton in good yields with a high enantioselectivity.
- Onodera, Gen,Nishibayashi, Yoshiaki,Uemura, Sakae
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p. 3819 - 3822
(2007/10/03)
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- Direct β-alkylation of secondary alcohols with primary alcohols catalyzed by a Cp*Ir complex
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(Chemical Equation Presented) A new catalytic system for β-alkylation of secondary alcohols has been developed. In the presence of [Cp*IrCl 2]2 (Cp* = pentamethylcyclopentadienyl) catalyst and base, the reactions of various secondary alcohols with primary alcohols give β-alkylated higher alcohols in good to excellent yields without any hydrogen acceptor or hydrogen donor. This reaction proceeds via successive hydrogen-transfer reactions and aldol condensation.
- Fujita, Ken-Ichi,Asai, Chiho,Yamaguchi, Tetsuhiro,Hanasaka, Fumihiro,Yamaguchi, Ryohei
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p. 4017 - 4019
(2007/10/03)
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- Hydrogen transfer type oxidation of alcohols by rhodium and ruthenium catalyst under microwave irradiation
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Secondary alcohols were converted into the corresponding ketones by methyl acrylate and rhodium catalyst efficiently under microwave irradiation. Treatment of primary alcohols with the same condition resulted in the recovery of the starting materials. Primary alcohols were converted into aldehydes by hydrogen transfer reaction using methyl vinyl ketone and ruthenium catalyst under microwave irradiation.
- Takahashi, Masaaki,Oshima, Koichiro,Matsubara, Seijiro
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p. 9201 - 9204
(2007/10/03)
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- Palladium-catalyzed intermolecular hydroamination of alkynes: A dramatic rate-enhancement effect of o-aminophenol
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The hydroamination of alkynes using o-aminophenol proceeds in very high to good yields in the presence of Pd(NO3)2 catalyst. Remarkable rate enhancement with o-aminophenol is presumably due to the chelation effect of the ortho OH group to palladium. Copyright
- Shimada, Tomohiro,Yamamoto, Yoshinori
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p. 12670 - 12671
(2007/10/05)
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- Efficient acylation of toluene and anisole with aliphatic carboxylic acids catalysed by heteropoly salt Cs2.5H0.5PW12O40
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Heteropoly salt Cs2.5H0.5PW12O40 is a highly efficient and reusable solid acid catalyst for the liquid-phase acylation of toluene or anisole with C2 - C12 aliphatic carboxylic acids.
- Kaur, Jaspal,Kozhevnikov, Ivan V.
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p. 2508 - 2509
(2007/10/03)
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- One-pot synthesis of ketones using N-methoxy-N-methyl-2-pyridyl urethane
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The one-pot reaction of N-methoxy-N-methyl-2-pyridyl urethane with Grignard and organolithium reagents provided an efficient method for the preparation of unsymmetrical ketones.
- Lee, Na Ra,Lee, Jae In
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p. 1249 - 1255
(2007/10/03)
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- The catalytic Friedel-Crafts acylation reaction of aromatic compounds with carboxylic anhydrides using combined catalyst system of titanium(IV) chloride tris(trifluoromethanesulfonate) and trifluoromethanesulfonic acid
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Various aromatic ketones are prepared in good to high yields with carboxylic anhydrides using combined catalyst system of TiCl(OTf)3 and TfOH.
- Izumi, Jun,Mukaiyama, Teruaki
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p. 739 - 740
(2007/10/03)
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- Friedel-Crafts Acylation of Arenes Catalysed by Bromopentacarbonylrhenium(I)
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The intermolecular Friedel-Crafts acylation of aromatic compounds (such as toluene, m-xylene, and anisole) with various acid chlorides proceeds by using a catalytic amount of bromopentacarbonylrhenium(I) to afford aryl ketones.Intramolecular acylation is also catalyzed by the above-mentioned catalyst to give indanone and tetralone derivatives.
- Kusama, Hiroyuki,Narasaka, Koichi
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p. 2379 - 2384
(2007/10/03)
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