176853-41-1Relevant articles and documents
Biocatalytic reduction of α,β-unsaturated carboxylic acids to allylic alcohols
Aleku, Godwin A.,Leys, David,Roberts, George W.
, p. 3927 - 3939 (2020/07/09)
We have developed robust in vivo and in vitro biocatalytic systems that enable reduction of α,β-unsaturated carboxylic acids to allylic alcohols and their saturated analogues. These compounds are prevalent scaffolds in many industrial chemicals and pharmaceuticals. A substrate profiling study of a carboxylic acid reductase (CAR) investigating unexplored substrate space, such as benzo-fused (hetero)aromatic carboxylic acids and α,β-unsaturated carboxylic acids, revealed broad substrate tolerance and provided information on the reactivity patterns of these substrates. E. coli cells expressing a heterologous CAR were employed as a multi-step hydrogenation catalyst to convert a variety of α,β-unsaturated carboxylic acids to the corresponding saturated primary alcohols, affording up to >99percent conversion. This was supported by the broad substrate scope of E. coli endogenous alcohol dehydrogenase (ADH), as well as the unexpected CC bond reducing activity of E. coli cells. In addition, a broad range of benzofused (hetero)aromatic carboxylic acids were converted to the corresponding primary alcohols by the recombinant E. coli cells. An alternative one-pot in vitro two-enzyme system, consisting of CAR and glucose dehydrogenase (GDH), demonstrates promiscuous carbonyl reductase activity of GDH towards a wide range of unsaturated aldehydes. Hence, coupling CAR with a GDH-driven NADP(H) recycling system provides access to a variety of (hetero)aromatic primary alcohols and allylic alcohols from the parent carboxylates, in up to >99percent conversion. To demonstrate the applicability of these systems in preparative synthesis, we performed 100 mg scale biotransformations for the preparation of indole-3-aldehyde and 3-(naphthalen-1-yl)propan-1-ol using the whole-cell system, and cinnamyl alcohol using the in vitro system, affording up to 85percent isolated yield.
Effective and Sustainable Access to Quinolines and Acridines: A Heterogeneous Imidazolium Salt Mediates C–C and C–N Bond Formation
Gisbert, Patricia,Albert-Soriano, María,Pastor, Isidro M.
, p. 4928 - 4940 (2019/08/12)
Quinoline and acridine derivatives have been prepared using a functionalized imidazolium salt as heterogeneous catalyst. Different ketones have been coupled with 2-aminobenzaldehydes and 2-aminoaryl ketones under solvent-free conditions, employing 1,3-bis(carboxymethyl)-imidazolium chloride as a catalyst. The protocol is simple and effective for the synthesis of a variety of nitrogen containing heterocycles (> 35 examples) with moderate to excellent yields (up to 96 %), being possible to perform the reaction in preparative scale. Additionally, 3-acetylquinolines have been transformed, under solvent-free conditions, into quinolyl chalcone derivatives by means of the same catalyst. Thus, the catalytic system mediates both reactions effectively in a tandem procedure. Furthermore, the catalyst is easily separated from the reaction mixture and can be reused without loss of activity (up to 8 cycles) which remarks its sturdiness. The E-factors are in the range of 14–23, both for the formation of quinolines and for the tandem reaction, which demonstrates the sustainability of the protocols described.
Synthesis of benzoquinoline derivatives from formyl naphthylamines via Friedl?nder annulation under metal-free conditions
Malinowski, Zbigniew,Fornal, Emilia,Warpas, Anna,Nowak, Monika
, p. 1999 - 2011 (2018/09/25)
Abstract: The synthesis of benzoquinolines and benzoquinolinones via Friedl?nder-type condensation of aminonaphthalene carbaldehydes with (1) primary or secondary alcohols mediated by urea/KOH or with (2) diketones or β-ketoesters is described. The behavi
Versatile Barium and Calcium Imidazolium-Dicarboxylate Heterogeneous Catalysts in Quinoline Synthesis
Albert-Soriano, María,Trillo, Paz,Soler, Tatiana,Pastor, Isidro M.
supporting information, p. 6375 - 6381 (2017/12/01)
This article details the development of heterogeneous catalysts based on calcium and barium in combination with the organic linker 1,3-bis(carboxymethyl)imidazolium (bcmim). The linker and the materials from alkaline earth metals are easily prepared under very smooth conditions. The use of linkers with different counterions (Cl or Br) provided different materials. Calcium- and barium-based catalysts were successfully employed in the preparation of quinoline derivatives from ketones and 2-aminoarylaldehydes or 2-aminoarylketones. In general, barium-based catalysts provided better results than calcium, although the latter are an excellent complement for certain substrates. Thus, a notable feature of such catalysts is the possibility of accessing a variety of complementary heterogeneous catalytic systems, rendering the catalysis adaptive to the reactant.||||||.
Gold(I)-catalyzed unprecedented rearrangement reaction between 2-aminobenzaldehydes with propargyl amines: An expedient route to 3-aminoquinolines
Patil, Nitin T.,Raut, Vivek S.,Shinde, Valmik S.,Gayatri, Gaddamanugu,Sastry, G. Narahari
supporting information; experimental part, p. 5530 - 5535 (2012/05/21)
Access to aminoquinolines: A gold(I)-catalyzed unprecedented rearrangement reaction between 2-aminobenzaldehydes with propargyl amine was studied. The study provided, for the first time, direct access to 3-aminoquinolines in one step starting from readily available starting materials (see scheme). Elegantly designed experiments were employed to unravel the mechanism of this unprecedented rearrangement, which are corroborated by DFT calculations.
One-pot friedlnder quinoline synthesis: Scope and limitations
Li, An-Hu,Beard, David J.,Coate, Heather,Honda, Ayako,Kadalbajoo, Mridula,Kleinberg, Andrew,Laufer, Radoslaw,Mulvihill, Kristen M.,Nigro, Anthony,Rastogi, Pawan,Sherman, Dan,Siu, Kam W.,Steinig, Arno G.,Wang, Ti,Werner, Doug,Crew, Andrew P.,Mulvihill, Mark J.
experimental part, p. 1678 - 1686 (2010/06/22)
A highly effective one-pot Friedlnder quinoline synthesis from o-nitroarylcarbaldehydes and ketones or aldehydes was developed and the scope and limitations of the method were examined. The o-nitroarylcarbaldehydes were reduced to o-aminoarylcarbaldehydes with iron in the presence of a catalytic amount of aqueous hydrochloric acid; the amino compounds were then condensed in situ with ketones or aldehydes to form mono- or disubstituted quinolines, respectively, in good-to-excellent yields (58-100%). Georg Thieme Verlag Stuttgart - New York.
A facile synthesis of 2-methylquinolines via Pd-catalyzed aza-Wacker oxidative cyclization
Zhang, Zuhui,Tan, Jiajing,Wang, Zhiyong
, p. 173 - 175 (2008/09/18)
(Chemical Equation Presented) A novel Pd-catalyzed Wacker-type oxidative cyclization under air is described. By using this cyclization, a series of 2-methylquinolines are readily prepared with good yields under mild conditions.
A highly effective one-pot synthesis of quinolines from o-nitroarylcarbaldehydes
Li, An-Hu,Ahmed, Eilaf,Chen, Xin,Cox, Matthew,Crew, Andrew P.,Dong, Han-Qing,Jin, Meizhong,Ma, Lifu,Panicker, Bijoy,Siu, Kam W.,Steinig, Arno G.,Stolz, Kathryn M.,Tavares, Paula A. R.,Volk, Brian,Weng, Qinghua,Werner, Doug,Mulvihill, Mark J.
, p. 61 - 64 (2008/03/14)
A simple and an efficient one-pot quinoline synthesis using inexpensive and readily available reagents was proposed. The solids were removed by filtration and the filtrate was treated with ketone and powdered KOH. The o-Nitroarylcarbaldehydes were reduced to aminocarbaldehydes with iron in the presence of catalytic HCl and subsequently condensed in situ with aldehydes or ketones to form mono- or di-substituted quinolines in high yields. The method can be used to prepare 2,3-disubstituted quinolines. A mixture of isomers was generated when an unsymmetrical ketone was used, which proved to be easily separable by silica gel column chromatography. The one-pot procedure is mild enough to allow a phenyl-substituted α,β-unsaturated ketone for using as a reactant under basic conditions in refluxing ethanol without significant competition from 1,4-Michael addition. The method provides efficient means to synthesize biologically active natural and unnatural quinoline-derived compounds.
Introduction of benzo[h]quinoline and 1,10-phenanthroline subunits by friedl?nder methodology
Riesgo, Elvira C.,Jin, Xiaoqing,Thummel, Randolph P.
, p. 3017 - 3022 (2007/10/03)
An improved preparation of 8-amino-7-quinolinecarbaldehyde has been developed. The methyl group of 7-methyl-8-nitroquinoline may be oxidized to an aldehyde by treatment first with dimethylformamide dimethyl acetal followed by sodium periodate. Reduction with iron provides the amino aldehyde. An analogous sequence affords 1-amino-2-naphthalenecarbaldehyde. Friedl?nder condensation of the quinoline derivative with a series of acetylaromatics provides the corresponding 2-aryl-1,10-phenanthrolines. Condensation of either amino aldehyde with 1,3-diacetylbenzene or 2,6-diacetylpyridine provides the expected Friedl?nder product. Similar chemistry is described for reactions of the amino aldehydes with 1,4-diacetylbenzene, 4,4′-diacetylbiphenyl, 1,5-diacetylanthracene, 1,2,3,4,5,6,7,8-octahydroacridine-1,8-dione, and tetracyclo-[6.3.0.0.4,1105,9]undecane-2,7-dione (TCU-2,7-dione).
