- Hydrazine Hydrate Accelerates Neocuproine–Copper Complex Generation and Utilization in Alkyne Reduction, a Significant Supplement Method for Catalytic Hydrogenation
-
Diimine (HN═NH) is a strong reducing agent, but the efficiency of diimine oxidized from hydrazine hydrate or its derivatives is still not good enough. Herein, we report an in situ neocuproine–copper complex formation method. The redox potential of this complex enable it can serve as an ideal redox catalyst in the synthesis of diimine by oxidation of hydrazine hydrate, and we successfully applied this technique in the reduction of alkynes. This reduction method displays a broad functional group tolerance and substrate adaptability as well as the advantages of safety and high efficiency. Especially, nitro, benzyl, boc, and sulfur containing alkynes can be reduced to the corresponding alkanes directly, which provides a useful complementary method to traditional catalytic hydrogenation. Besides, we applied this method in the preparation of the Alzheimer’s disease drug CT-1812 and studied the mechanism.
- Chen, Guoliang,He, Xiaoyan,Huang, Gang,Lu, Xiuhong,Wang, Jincheng,Yang, Zhenjiao,Zhang, Yongsheng,Zhang, Zeng
-
p. 17696 - 17709
(2021/12/09)
-
- Generalized Chemoselective Transfer Hydrogenation/Hydrodeuteration
-
A generalized, simple and efficient transfer hydrogenation of unsaturated bonds has been developed using HBPin and various proton reagents as hydrogen sources. The substrates, including alkenes, alkynes, aromatic heterocycles, aldehydes, ketones, imines, azo, nitro, epoxy and nitrile compounds, are all applied to this catalytic system. Various groups, which cannot survive under the Pd/C/H2 combination, are tolerated. The activity of the reactants was studied and the trends are as follows: styrene'diphenylmethanimine'benzaldehyde'azobenzene'nitrobenzene'quinoline'acetophenone'benzonitrile. Substrates bearing two or more different unsaturated bonds were also investigated and transfer hydrogenation occurred with excellent chemoselectivity. Nano-palladium catalyst in situ generated from Pd(OAc)2 and HBPin extremely improved the TH efficiency. Furthermore, chemoselective anti-Markovnikov hydrodeuteration of terminal aromatic olefins was achieved using D2O and HBPin via in situ HD generation and discrimination. (Figure presented.).
- Wang, Yong,Cao, Xinyi,Zhao, Leyao,Pi, Chao,Ji, Jingfei,Cui, Xiuling,Wu, Yangjie
-
supporting information
p. 4119 - 4129
(2020/08/10)
-
- Rh-Catalyzed C-H Amination/Annulation of Acrylic Acids and Anthranils by Using -COOH as a Deciduous Directing Group: An Access to Diverse Quinolines
-
A method for the synthesis of diverse polysubstituted quinolines from readily available acrylic acids and anthranils has been developed. The weakly coordinating -COOH directing group, which can be tracelessly removed in the cascade cyclization, is essential for this reaction. Diverse polysubstituted quinolines were obtained under mild reaction conditions with simple H2O and CO2 as byproducts. More importantly, 1,2,3,4-tetrahydroacridine, which is the core skeleton of tacrine (an Alzheimer's disease drug), was conveniently synthesized.
- Gao, Yang,Nie, Jianhong,Li, Yibiao,Li, Xianwei,Chen, Qian,Huo, Yanping,Hu, Xiao-Qiang
-
supporting information
p. 2600 - 2605
(2020/04/02)
-
- Pd-Catalyzed Alkylation of (Iso)quinolines and Arenes: 2-Acylpyridine Compounds as Alkylation Reagents
-
The first Pd-catalyzed alkylation of (iso)quinolines and arenes is reported. The readily available and bench-stable 2-acylpyridine compounds were used as an alkylation reagent to form the structurally versatile alkylated (iso)quinolines and arenes. The method affords a convenient pathway for the introduction of alkyl groups into organic molecules.
- Wu, Qingsong,Han, Shuaijun,Ren, Xiaoxiao,Lu, Hongtao,Li, Jingya,Zou, Dapeng,Wu, Yangjie,Wu, Yusheng
-
supporting information
p. 6345 - 6348
(2018/10/20)
-
- 4,5,6,7-TETRAHYDRO-1 H-PYRAZOLO[4,3-C]PYRIDIN-3-AMINE COMPOUNDS AS CBP AND/OR EP300 INHIBITORS
-
The present invention relates to compounds of formula (I) or formula (II): and to salts thereof, wherein R1-R4 of formula (I) and R1-R3 of formula (II) have any of the values defined herein, and compositions and uses thereof. The compounds are useful as inhibitors of CBP and/or EP300. Also included are pharmaceutical compositions comprising a compound of formula (I) of formula (II) or a pharmaceutically acceptable salt thereof, and methods of using such compounds and salts in the treatment of various CBP and/or EP300-mediated disorders.
- -
-
Page/Page column 238; 239
(2016/06/14)
-
- Metal-free aerobic one-pot synthesis of substituted/annulated quinolines from alcohols via indirect Friedl?nder annulation
-
Metal-free, operationally simple, and highly efficient one-pot aerobic process for the synthesis of functionalized/annulated quinolines is devised from easily available 2-aminobenzyl alcohol/2-aminobenzophenones and alkyl/aryl alcohols for the first time. The process involves two sequential reactions, namely in situ aerial oxidation of alcohols to the corresponding aldehydes/ketones followed by Friedl?nder annulation.
- Anand, Namrata,Koley, Suvajit,Ramulu, B. Janaki,Singh, Maya Shankar
-
supporting information
p. 9570 - 9574
(2015/09/28)
-
- On-line reaction monitoring and mechanistic studies by mass spectrometry: Negishi cross-coupling, hydrogenolysis, and reductive amination
-
Reaction monitoring using inductive ESI mass spectrometry allows chemical reactions to be tracked in real time, including air- and moisture-sensitive as well as heterogeneous reactions. Highly concentrated solutions can also be monitored for long periods without emitter clogging. Sheath gas assists in nebulization and a sample splitter reduces the delay time and minimizes contamination of the instrument. Short-lived intermediates (ca. 5 s) were observed in Pd/C-catalyzed hydrogenolysis, and several intermediates were seen in Negishi cross-coupling reactions. Fast and simple: A reaction monitoring system based on inductive ESI mass spectrometry provides a fast and simple way to monitor chemical reactions, including air-/moisture-sensitive reactions, continuously. It also provides information on solution-phase organic reaction mechanisms as shown by the observation of short-lived intermediates in Pd/C-catalyzed hydrogenolysis and several intermediates in Negishi cross-coupling reactions.
- Yan, Xin,Sokol, Ewa,Li, Xin,Li, Guangtao,Xu, Shiqing,Cooks, R. Graham
-
supporting information
p. 5931 - 5935
(2014/06/10)
-
- Direct B-alkyl Suzuki-Miyaura cross-coupling of trialkyl-boranes with aryl bromides in the presence of unmasked acidic or basic functions and base-labile protections under mild non-aqueous conditions
-
An efficient and chemoselective palladium-catalyzed direct B-alkyl Suzuki-Miyaura cross-coupling of trialkylboranes with diversely functionalized aryl bromides is described. A wide variety of unmasked acidic or basic functions are tolerated. The mild non-
- Wang, Bing,Sun, Hui-Xia,Sun, Zhi-Hua,Lin, Guo-Qiang
-
experimental part
p. 415 - 422
(2009/10/23)
-
- Fast and convenient base-mediated synthesis of 3-substituted quinolines
-
In a convenient method, 3-substituted quinolines are readily synthesized in a two-step process with initial oxazine formation and subsequent base-mediated cyclization.
- Mierde, Hans Vander,Voort, Pascal Van Der,Verpoort, Francis
-
scheme or table
p. 201 - 203
(2009/04/19)
-
- New gas-phase cascade reactions of stabilized phosphorus ylides leading to ring-fused indoles and to quinolines
-
(Chemical Equation Presented) Gas-phase cyclization processes of stabilized phosphorus ylides bearing a suitably substituted 2-aminophenyl group lead efficiently either to 3-substituted quinolines or benzo[c]-carbazole and heterocyclic-fused analogues depending on the substituents present.
- Aitken, R. Alan,Murray, Lorna
-
supporting information; experimental part
p. 9781 - 9783
(2009/04/06)
-
- A NOVEL REDUCTIVE DEHALOGENATION USING POTASSIUM HYDROXIDE/POLYETHYLENE GLYCOL (400)/XYLENE MIXTURES
-
Various halogeno-compounds underwent reductive dehalogenation reaction under the action of KOH/Polyethylene glycol (400) in boiling xylene in high yield.
- El Massry, Abdel Moneim,Amer, Adel,Pittman, Charles U.
-
p. 1091 - 1094
(2007/10/02)
-
- Ozonolysis of Quinolines: A Versatile Synthesis of Polyfunctional Pyridines
-
A simple, safe and efficient procedure, easily adapted to a large scale, is described for the synthesis of substituted quinolines 2, which are readily oxidized by ozone in the presence of mineral acid, followed by an oxidative work up with hydrogen peroxide to afford substituted 2,3-pyridinedicarboxylic acids 3a-d,f and acyl pyridines 3e, g.
- O'Murchu, C.
-
p. 880 - 882
(2007/10/02)
-
- PREPARATION OF 3-SUBSTITUTED QUINOLINES. II. PREPARATION AND CYCLODEHYDRATION OF α-ALKYL- AND α-PHENYL-β-ARYLAMINOACROLEIN DERIVATIVES
-
α-Methyl-β-arylaminoacroleins were prepared by the hydrolysis of 2-methyl-1-arylamino-3-arylimino-1-propene derivatives. α-Ethyl- and α-phenyl-β-arylaminoacroleins were prepared by the reaction of arylamine and 2-substituted 1,1,3,3-tetraethoxypropane derivatives. 3-Methyl, 3-ethyl- and 3-phenylquinolines were obtained from α-methyl-, α-ethyl and α-phenyl-β-arylaminoacroleins on heating with aluminum bromide in good yields. α-Bromo-β-anilinoacrolein (9b) was prepared by the reaction of β-anilinoacrolein (6b) and N-bromosuccinimide.Reaction of 9b and aluminum bromide did not afford 3-bromoquinoline.
- Todoriki, Reiko,Ono, Machiko,Tamura, Shinzo
-
p. 755 - 769
(2007/10/02)
-