1669-33-6Relevant articles and documents
Iron-Catalyzed C-C Single-Bond Cleavage of Alcohols
Liu, Wei,Wu, Qiang,Wang, Miao,Huang, Yahao,Hu, Peng
supporting information, p. 8413 - 8418 (2021/11/01)
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.
Chemoselective Synthesis of Aryl Ketones from Amides and Grignard Reagents via C(O)-N Bond Cleavage under Catalyst-Free Conditions
Sureshbabu, Popuri,Azeez, Sadaf,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
, p. 11823 - 11838 (2019/10/02)
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.
Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedl?nder Quinoline Synthesis
Barman, Milan K.,Jana, Akash,Maji, Biplab
supporting information, p. 3233 - 3238 (2018/07/31)
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.).
Syntheses, structures, and catalytic activity in Friedel–Crafts acylations of substituted tetramethylcyclopentadienyl molybdenum carbonyl complexes
Li, Tong,Yan, Xin-Long,Li, Zhan-Wei,Ma, Zhi-Hong,Li, Su-Zhen,Han, Zhan-Gang,Zheng, Xue-Zhong,Lin, Jin
, p. 313 - 322 (2018/02/22)
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.
RhCl(CO)(PPh3)2 catalyzed α-alkylation of ketones with alcohols
Wang, Rui,Huang, Lina,Du, Zhengyin,Feng, Hua
supporting information, p. 40 - 43 (2017/06/07)
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.
Acyl hydrazides as acyl donors for the synthesis of diaryl and aryl alkyl ketones
Akhbar, Ahmed R.,Chudasama, Vijay,Fitzmaurice, Richard J.,Powell, Lyn,Caddick, Stephen
, p. 743 - 746 (2014/01/06)
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.
Direct α-alkylation of ketones with alcohols in water
Xu, Guoqiang,Li, Qiong,Feng, Jiange,Liu, Qiang,Zhang, Zuojun,Wang, Xicheng,Zhang, Xiaoyun,Mu, Xindong
, p. 105 - 109 (2014/03/21)
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.
An Efficient α-alkylation of aromatic ketones with primary alcohols catalyzed by [cp*ircl2]2 without solvent
Li, Jian,Zhang, Weixing,Wang, Feng,Jiang, Min,Dong, Xiaochun,Zhao, Weili
, p. 2363 - 2366,4 (2020/09/16)
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
Direct acylation of aryl bromides with aldehydes by palladium catalysis
Ruan, Jiwu,Saidi, Ourida,Iggo, Jonathan A.,Xiao, Jianliang
supporting information; experimental part, p. 10510 - 10511 (2009/02/05)
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
Ir- and Ru-catalyzed sequential reactions: Asymmetric α-alkylative reduction of ketones with alcohols
Onodera, Gen,Nishibayashi, Yoshiaki,Uemura, Sakae
, p. 3819 - 3822 (2007/10/03)
(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.
