1083-30-3Relevant academic research and scientific papers
Acylation of α-aminoalkyl- copper and cuprate reagents with acid chlorides: Improved yields with soluble copper (I) salts
Dieter, R. Karl,Sharma, Ram R.,Ryan, Wendy
, p. 783 - 786 (1997)
α-Aminoalkylcopper reagents prepared from soluble CuX·2LiCI give modest to good yields of α-aminoketones upon reaction with acid chlorides, Higher yields are generally obtained with CuCl·2LiCl than with CuCN·2LiCl. Improved yields can be obtained by utilization of cuprate reagents prepared from CuCN·2LiCl and 2.0 equivalents of α-lithiocarbamates.
Green alcohol couplings without transition metal catalysts: Base-mediated β-alkylation of alcohols in aerobic conditions
Allen, Laura J.,Crabtree, Robert H.
, p. 1362 - 1364 (2010)
Benzylic secondary alcohols can be alkylated in good yields at the β-position with primary alcohols promoted by KOH and NaOH, eliminating the need for toxic and expensive transition metal catalysts.
Sustainable and Selective Alkylation of Deactivated Secondary Alcohols to Ketones by Non-bifunctional Pincer N-heterocyclic Carbene Manganese
Lan, Xiao-Bing,Ye, Zongren,Liu, Jiahao,Huang, Ming,Shao, Youxiang,Cai, Xiang,Liu, Yan,Ke, Zhuofeng
, p. 2557 - 2563 (2020)
A sustainable and green route to access diverse functionalized ketones via dehydrogenative–dehydrative cross-coupling of primary and secondary alcohols is demonstrated. This borrowing hydrogen approach employing a pincer N-heterocyclic carbene Mn complex displays high activity and selectivity. A variety of primary and secondary alcohols are well tolerant and result in satisfactory isolated yields. Mechanistic studies suggest that this reaction proceeds via a direct outer-sphere mechanism and the dehydrogenation of the secondary alcohol substrates plays a vital role in the rate-limiting step.
NAD(P)+-NAD(P)H Model. 62. The Mechanism of the Silica Gel-Catalyzed Reduction with an NAD(P)H Model
Yasui, Shinro,Fujii, Masayuki,Nakamura, Kaoru,Ohno, Atsuyoshi
, p. 963 - 968 (1987)
The reduction of diethyl acetylenedicarboxylate, diethyl fumarate, and diethyl maleate as well as several α,β-unsaturated carbonyl compounds by a model of NAD(P)H on silica gel was examined.The order of the reactivity for the reduction was reverse to that of the degree of adsorption of the substrates onto the surface of silica gel.Semiquantitative analysis of the results suggests the possibility that silanol groups on the surface of silica gel act as general acid catalysts in the course of the reduction.
Unexpected double benzylation of acetophenone under phase transfer catalysis conditions, acidity or π-π interaction effect?
Diez-Barra, Enrique,De la Hoz, Antonio,Loupy, Andre,Martinez-Gonzalez, Alfonso,Martinez-Merino, Victor,Merino, Sonia,Paugam, Renee,Sanchez-Verdu, Prado,Sansoulet, Jean,Torres, Jose
, p. 3659 - 3668 (1997)
A π-π interaction in the transition state of the benzylation of 1,3-diphenyl-1-propanone, the monobenzylation product of acetophenone, is proposed according to chemical, kinetic and theoretical approaches. Evidence for the existence of this kind of interaction in a transition state has been provided for the first time. The results obtained cannot be explained solely by the increased acidity but by considering the existence of a π-π interaction.
Metal Carbonyl-Induced N-O Bond Cleavage of the Oxime Group
Nitta, Makoto,Iino, Yukio
, p. 2365 - 2367 (1986)
The reaction of or with oxime O-acetate of 1,3-diphenyl-2-propen-1-one undergoes a reductive N-O bond cleavage to give an imine which dimerises and/or is hydrolyzed to ketones.The dimer, so formed, undergoes fragmentations to give pyridine and pyrimidine derivatives.Similarly, the reaction of with several oxime O-acetates, oximes, and an oxime ether were shown to give the corresponding ketones.A reaction of oxime O-acetates with or with to give the corresponding ketones was also shown to proceed very slowly.
Synthesis of a-Alkylated Ketones via Tandem Acceptorless Dehydrogenation/a-Alkylation from Secondary and Primary Alcohols Catalyzed by Metal-Ligand Bifunctional Iridium Complex [CpIr(2,2′-bpyO)(H2O)]
Wang, Rongzhou,Ma, Juan,Li, Feng
, p. 10769 - 10776 (2015)
A new strategy for the synthesis of α-alkylated ketones via tandem acceptorless dehydrogenation/α-alkylation from secondary and primary alcohols was proposed and accomplished. In the presence of metal-ligand bifunctional iridium complex [CpIr(2,2′-bpyO)(H2O)], various desirable products were obtained in high yields. Compared with previous methods for the direct dehydrogenative coupling of secondary alcohols with primary alcohols to α-alkylated ketones, this protocol has obvious advantages including complete selectivity for α-alkylated ketones and more environmentally benign conditions. Notably, the study also exhibited the potential to develop tandem reactions catalyzed using a metal-ligand bifunctional iridium complex.
Pyracene-linked bis-imidazolylidene complexes of palladium and some catalytic benefits produced by bimetallic catalysts
Guisado-Barrios, Gregorio,Hiller, Joanna,Peris, Eduardo
, p. 10405 - 10411 (2013)
Two new palladium complexes with a pyracene-linked bis-imidazolylidene (pyrabim) group have been obtained and fully characterized. The related monometallic analogues were obtained from the coordination of an acetanaphthene-supported N-heterocyclic carbene
NAD(P)+-NAD(P)H Models. 64. The Quantitative Elucidation of the Mechanistic Aspects in the Silica Gel-Catalyzed Reduction of α,β-Unsaturated Carbonyl Compounds by a Model of NAD(P)H
Yasui, Shinro,Fujii, Masayuki,Ohno, Atsuyoshi
, p. 4019 - 4026 (1987)
Eight α,β-unsaturated carbonyl compounds, 1-(2'- or 4'-substituted phenyl)-3-phenyl-2-propen-1-ones (2'-or 4'-substituted chalcones), were subjected to the reduction by an NAD(P)H model in the presence of silica gel in benzene.All of these afforded quantitatively the corresponding saturated carbonyl compounds, whereas no 1,2-reduction took place.For 2'-methoxy, 4'-methyl, 4'-bromo, and 4'-nitro derivatives as well as the unsubstituted carbonyl compound, the apparent reactivity of the substrate increases with the increase in electronwithdrawing ability of the substituent, whereas the degree of the adsorption onto the surface of silica gel decreases.It is also apparent that the 4'-hydroxy derivative exerts lower reactivity than the 2'-hydroxy derivative in spite of much more efficient adsorption of the former.In order to uniformly interpret the apparent results, the data obtained were quantitatively analyzed in terms of kinetics as well as equilibrium constants for the adsorption of the substrates onto the surface of silica gel.It has been revealed that the silanol group on the surface of silica gel acts as a general-acid catalyst in the reduction.
Cu-Ag/hydrotalcite catalysts for dehydrogenative cross-coupling of primary and secondary benzylic alcohols
Xu, Jin,Yue, Hongmei,Liu, Sheng,Wang, Hanfei,Du, Yuqun,Xu, Chunli,Dong, Wensheng,Liu, Chunling
, p. 24164 - 24174 (2016)
The development of new and inexpensive heterogeneous catalysts for direct C-C cross-coupling of primary and secondary alcohols is a challenging goal and has great importance in academic and industrial sectors. In this work Cu-Ag/hydrotalcite (Cu-Ag/HT) catalysts were prepared and tested for their impact on this cross-coupling. The effect of supports, including MgO, γ-Al2O3 and HT with different Mg : Al molar ratios, was investigated. It was found that the acidic or basic properties of the supports affected product selectivity. The roles of Cu and Ag sites in the cross-coupling were also investigated with the prepared Cu-Ag/HT catalyst demonstrating high activity and selectivity for the reaction. The yield-to-target product of β-phenylpropiophenone reached 99% after 1 h under optimum reaction conditions. The stability in air and reusability studies show that Cu-Ag/HT can be stored for 6 days and can be used five times without apparent deactivation, respectively.
