20359-57-3Relevant academic research and scientific papers
Combined Theoretical and Experimental Studies Unravel Multiple Pathways to Convergent Asymmetric Hydrogenation of Enamides
Yang, Jianping,Massaro, Luca,Krajangsri, Suppachai,Singh, Thishana,Su, Hao,Silvi, Emanuele,Ponra, Sudipta,Eriksson, Lars,Ahlquist, M?rten S. G.,Andersson, Pher G.
supporting information, p. 21594 - 21603 (2021/12/27)
We present a highly efficient convergent asymmetric hydrogenation of E/Z mixtures of enamides catalyzed by N,P-iridium complexes supported by mechanistic studies. It was found that reduction of the olefinic isomers (E and Z geometries) produces chiral amides with the same absolute configuration (enantioconvergent hydrogenation). This allowed the hydrogenation of a wide range of E/Z mixtures of trisubstituted enamides with excellent enantioselectivity (up to 99% ee). A detailed mechanistic study using deuterium labeling and kinetic experiments revealed two different pathways for the observed enantioconvergence. For α-aryl enamides, fast isomerization of the double bond takes place, and the overall process results in kinetic resolution of the two isomers. For α-alkyl enamides, no double bond isomerization is detected, and competition experiments suggested that substrate chelation is responsible for the enantioconvergent stereochemical outcome. DFT calculations were performed to predict the correct absolute configuration of the products and strengthen the proposed mechanism of the iridium-catalyzed isomerization pathway.
I-Pr2NMgCl·LiCl Enables the Synthesis of Ketones by Direct Addition of Grignard Reagents to Carboxylate Anions
Colas, Kilian,Dos Santos, A. Catarina V. D.,Mendoza, Abraham
supporting information, (2019/10/08)
The direct preparation of ketones from carboxylate anions is greatly limited by the required use of organolithium reagents or activated acyl sources that need to be independently prepared. Herein, a specific magnesium amide additive is used to activate and control the addition of more tolerant Grignard reagents to carboxylate anions. This strategy enables the modular synthesis of ketones from CO2 and the preparation of isotopically labeled pharmaceutical building blocks in a single operation.
Directed: Ortho-metalation-nucleophilic acyl substitution strategies in deep eutectic solvents: The organolithium base dictates the chemoselectivity
Ghinato, Simone,Dilauro, Giuseppe,Perna, Filippo Maria,Capriati, Vito,Blangetti, Marco,Prandi, Cristina
, p. 7741 - 7744 (2019/07/12)
Directed ortho metalation (DoM) or nucleophilic acyl substitution (SNAc) can be efficiently programmed on the same aromatic carboxylic acid amide, in a choline chloride-based eutectic mixture, by simply switching the nature of the organolithium reagent. Telescoped, one-pot ortho-lithiation/Suzuki-Miyaura cross-couplings have also been demonstrated for the first time in Deep Eutectic Solvents.
Pd-catalyzed Oxidative Cross-coupling of Alkyl Chromium(0) Fischer Carbene Complexes with Organoboronic Acids
Wang, Kang,Yang, Jinghui,Yao, Xingqi,Wang, Jianbo
supporting information, p. 3165 - 3168 (2018/10/15)
Alkyl chromium(0) carbene complexes have been explored as the cross-coupling partners in the palladium-catalyzed reaction with aryl or alkenyl boronic acids. This coupling reaction displays the versatile reactivities of alkyl chromium(0) carbenes under palladium catalysis. Mechanistically, this transformation is proposed to involve deprotonation of the alkyl chromium carbene substrate to generate a vinyl chromium anion intermediate that undergoes transmetalation to organopalladium species and reductive elimination.
A phosphine-free, heterogeneous palladium-catalyzed atom-efficient carbonylative cross-coupling of triorganoindiums with aryl halides leading to unsymmetrical ketones
You, Shengyong,Xiao, Ruian,Liu, Haiyi,Cai, Mingzhong
, p. 13862 - 13870 (2017/11/27)
The first phosphine-free heterogeneous palladium-catalyzed carbonylative cross-coupling of aryl halides with triorganoindiums has been developed that proceeds smoothly under 1 or 2.5 atm of carbon monoxide in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable unsymmetrical ketones with high atom-economy, good yield, and recyclability of the catalyst. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
A phosphine-free, atom-efficient cross-coupling reaction of triorganoindiums with acyl chlorides catalyzed by immobilization of palladium(0) in MCM-41
Miao, Jiankang,Huang, Bin,Liu, Haiyi,Cai, Mingzhong
, p. 42570 - 42578 (2017/09/11)
The first phosphine-free heterogeneous palladium(0)-catalyzed cross-coupling of triorganoindiums with acyl chlorides has been developed that proceeds smoothly in THF at 68 °C and provides a general and powerful tool for the synthesis of various valuable aryl ketones and α,β-acetylenic ketones with high atom-economy and high yield. This phosphine-free heterogeneous palladium(0) catalyst can be easily prepared from commercially available reagents and recovered by a simple filtration of the reaction solution and used for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.
CERAMIDE GALACTOSYLTRANSFERASE INHIBITORS FOR THE TREATMENT OF DISEASE
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Paragraph 000505; 000506; 000598; 000599, (2018/01/17)
Described herein are compounds, methods of making such compounds, pharmaceutical compositions and medicaments containing such compounds, and methods of using such compounds to treat or prevent diseases or disorders associated with the enzyme ceramide galactosyltransferase (CGT), such as, for example, lysosomal storage diseases. Examples of lysosomal storage diseases include, for example, Krabbe disease and Metachromatic Leukodystrophy.
Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
, p. 4420 - 4424 (2014/06/10)
Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
A Palladium Bipyridyl Complex Grafted onto Nanosized MCM-41 as a Heterogeneous Catalyst for Negishi Coupling
Wu, Wei-Yi,Lin, Tze-Chiao,Takahashi, Tamotsu,Tsai, Fu-Yu,Mou, Chung-Yuan
, p. 1011 - 1019 (2013/05/09)
The Negishi coupling of aryl bromides or acyl chlorides with organozinc chlorides catalyzed by a palladium bipyridyl complex anchored on nanosized mobile crystalline material 41 (MCM-41) were investigated. The reactions proceeded smoothly with a very low catalyst loading in THF at 70°C for electron-deficient aryl bromides, which gave good to high yields of the Negishi coupling products. However, reactions in toluene at 110°C were required if electron-rich aryl bromides were employed. For acyl chlorides, the reactions could be performed in THF at 50°C and the corresponding ketones and ynones were obtained in high yields. After centrifugation, it was possible to easily recover the supported catalyst from the reaction mixture, and this could be reused several times without any retreatment or regeneration with only a slight decrease in activity.
An effective one-pot conversion of acid chlorides to aldehydes and ketones
Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
, p. 3199 - 3203 (2013/06/27)
Aldehydes and ketones were synthesized from their respective acid chlorides via a one-pot protocol. Morpholine amide intermediates that were readily prepared by the aminolysis of various acid chlorides with diisobutyl(morpholino) aluminum smoothly reacted with the reducing agent LDBMA and the organolithium reagents under mild reaction conditions (0 C), giving almost excellent product yields of up to 95%.
