scholarly journals Visible-light photoredox-catalyzed umpolung carboxylation of carbonyl compounds with CO2

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Guang-Mei Cao ◽  
Xin-Long Hu ◽  
Li-Li Liao ◽  
Si-Shun Yan ◽  
Lei Song ◽  
...  
Keyword(s):  
Visible Light ◽  
Carbonyl Compounds ◽  
High Selectivity ◽  
Reaction Conditions ◽  
Alkyl Aryl ◽  
Aryl Aldehydes ◽  
Hydroxycarboxylic Acids ◽  
Aryl Ketones ◽  
Carbon Radicals

AbstractPhotoredox-mediated umpolung strategy provides an alternative pattern for functionalization of carbonyl compounds. However, general approaches towards carboxylation of carbonyl compounds with CO2 remain scarce. Herein, we report a strategy for visible-light photoredox-catalyzed umpolung carboxylation of diverse carbonyl compounds with CO2 by using Lewis acidic chlorosilanes as activating/protecting groups. This strategy is general and practical to generate valuable α-hydroxycarboxylic acids. It works well for challenging alkyl aryl ketones and aryl aldehydes, as well as for α-ketoamides and α-ketoesters, the latter two of which have never been successfully applied in umpolung carboxylations with CO2 (to the best of our knowledge). This reaction features high selectivity, broad substrate scope, good functional group tolerance, mild reaction conditions and facile derivations of products to bioactive compounds, including oxypheonium, mepenzolate bromide, benactyzine, and tiotropium. Moreover, the formation of carbon radicals and carbanions as well as the key role of chlorosilanes are supported by control experiments.

Multiple arylation of alkyl aryl ketones and α,β-unsaturated carbonyl compounds via palladium catalysis

Tetrahedron ◽  
2001 ◽  
Vol 57 (28) ◽  
pp. 5967-5974 ◽  
Author(s):  
Yoshito Terao ◽  
Yoko Kametani ◽  
Hiroyuki Wakui ◽  
Tetsuya Satoh ◽  
Masahiro Miura ◽  
...  
Keyword(s):  
Carbonyl Compounds ◽  
Palladium Catalysis ◽  
Alkyl Aryl ◽  
Aryl Ketones

scholarly journals The A3 Redox-Neutral C1-Alkynylation of Tetrahydroisoquinolines: A Comparative Study between Visible Light Photocatalysis and Transition-Metal Catalysis

Synthesis ◽  
2020 ◽  
Author(s):  
Vladimir V. Kouznetsov ◽  
Marlyn C. Ortiz Villamizar ◽  
Carlos E. Puerto Galvis
Keyword(s):  
Transition Metal ◽  
Microwave Irradiation ◽  
Visible Light ◽  
High Selectivity ◽  
Transition Metal Catalysis ◽  
Visible Light Photocatalysis ◽  
Reaction Conditions ◽  
Metal Catalysis ◽  
New Compounds ◽  
Optimal Reaction

AbstractConsidering the current challenges of the A3 redox-neutral C1-alkynylation of tetrahydroisoquinolines (THIQs), we studied this synthetic tool under visible light photocatalysis and transition-metal catalysis in order to describe alternative reaction conditions and discuss possible improvements to this process. We demonstrated that 1-alkynylated THIQs can be readily obtained by three different approaches: iridium-based photocatalysis and copper ([CuBr(PPh3)3]) and silver (AgNO3) catalysis under mild, selective and accessible reaction conditions. Among these approaches, the copper(I)-based methodology resulted in the most robust, optimal reaction conditions for the synthesis of a series of 18 1-alkynylated THIQs in moderate to excellent yields and with high selectivity for the endo-alkynylated products. Moreover, this reaction can be accelerated by microwave irradiation (120 °C, 15 min) affording a novel library of diverse THIQs with alkyne and N-substituent moieties, from unreactive and uncommon substrates, that could be further transformed into new compounds of interest.

scholarly journals Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilyl)methyl)aniline with cyclic α,β-unsaturated carbonyl compounds

2014 ◽  
Vol 10 ◽  
pp. 890-896 ◽  
Author(s):  
Dominik Lenhart ◽  
Thorsten Bach
Keyword(s):  
Visible Light ◽  
Carbonyl Compounds ◽  
Addition Reactions ◽  
Reaction Products ◽  
Reaction Conditions ◽  
Simple Addition ◽  
Tricyclic Compound ◽  
Major Reaction ◽  
Catalyzed Reactions ◽  
Carbonyl Radical

N-Methyl-N-((trimethylsilyl)methyl)aniline was employed as reagent in visible-light-induced, iridium-catalyzed addition reactions to cyclic α,β-unsaturated carbonyl compounds. Typical reaction conditions included the use of one equivalent of the reaction substrate, 1.5 equivalents of the aniline and 2.5 mol % (in MeOH) or 1.0 mol % (in CH2Cl2) [Ir(ppy)2(dtbbpy)]BF4 as the catalyst. Two major reaction products were obtained in combined yields of 30–67%. One product resulted from aminomethyl radical addition, the other product was a tricyclic compound, which is likely formed by attack of the intermediately formed α-carbonyl radical at the phenyl ring. For five-membered α,β-unsaturated lactone and lactam substrates, the latter products were the only products isolated. For the six-membered lactones and lactams and for cyclopentenone the simple addition products prevailed.

ChemInform Abstract: Multiple Arylation of Alkyl Aryl Ketones and α,β-Unsaturated Carbonyl Compounds via Palladium Catalysis.

ChemInform ◽  
2010 ◽  
Vol 32 (43) ◽  
pp. no-no
Author(s):  
Yoshito Terao ◽  
Yoko Kametani ◽  
Hiroyuki Wakui ◽  
Tetsuya Satoh ◽  
Masahiro Miura ◽  
...  
Keyword(s):  
Carbonyl Compounds ◽  
Palladium Catalysis ◽  
Alkyl Aryl ◽  
Aryl Ketones

Metal-Metal Cooperative Bond Activation by Heterobimetallic Alkyl, Aryl, and Acetylide PtII/CuI Complexes

2020 ◽  
Author(s):  
Shubham Deolka ◽  
Orestes Rivada Wheelaghan ◽  
Sandra Aristizábal ◽  
Robert Fayzullin ◽  
Shrinwantu Pal ◽  
...  
Keyword(s):  
Alkyl Group ◽  
Bond Activation ◽  
Bond Cleavage ◽  
Terminal Alkyne ◽  
Alkyl Aryl ◽  
Metal Metal ◽  
The Stability ◽  
Selective Formation ◽  
Organoplatinum Compounds

We report selective formation of heterobimetallic PtII/CuI complexes that demonstrate how facile bond activation processes can be achieved by altering reactivity of common organoplatinum compounds through their interaction with another metal center. The interaction of the Cu center with Pt center and with a Pt-bound alkyl group increases the stability of PtMe2 towards undesired rollover cyclometalation. The presence of the CuI center also enables facile transmetalation from electron-deficient tetraarylborate [B(ArF)4]- anion and mild C-H bond cleavage of a terminal alkyne, which was not observed in the absence of an electrophilic Cu center. The DFT study indicates that the role of Cu center acts as a binding site for alkyne substrate, while activating its terminal C-H bond.

Microbial Bioconversion: A Regio-specific Method for Novel Drug Design and Toxicological Study of Metabolites

2019 ◽  
Vol 20 (14) ◽  
pp. 1156-1162
Author(s):  
Maria Yousuf ◽  
Waqas Jamil ◽  
Khayala Mammadova
Keyword(s):  
Microbial Transformation ◽  
Specific Method ◽  
Reaction Conditions ◽  
Small Organic Molecules ◽  
Toxicological Studies ◽  
Drug Designing ◽  
Transformation Methods ◽  
Novel Drug

The methods of chemical structural alteration of small organic molecules by using microbes (fungi, bacteria, yeast, etc.) are gaining tremendous attention to obtain structurally novel and therapeutically potential leads. The regiospecific mild environmental friendly reaction conditions with the ability of novel chemical structural modification in compounds categorize this technique; a distinguished and unique way to obtain medicinally important drugs and their in vivo mimic metabolites with costeffective and timely manner. This review article shortly addresses the immense pharmaceutical importance of microbial transformation methods in drug designing and development as well as the role of CYP450 enzymes in fungi to obtain in vivo drug metabolites for toxicological studies.

The Merger of CF3SO2Na and Palladium Catalysis to Enable Decarboxylative Cross-Coupling for the Synthesis of Aromatic Ketones under Room Temperature

2021 ◽  
Author(s):  
Pan Xie ◽  
Cheng Xue ◽  
Cancan Wang ◽  
Dongdong Du ◽  
Sanshan Shi
Keyword(s):  
Visible Light ◽  
Room Temperature ◽  
Palladium Catalysis ◽  
Cross Coupling ◽  
Boronic Acids ◽  
Aromatic Ketones ◽  
Aryl Ketones ◽  
Oxocarboxylic Acids

A CF3SO2Na/Pd(OAc)2 co-catalyzed strategy is developed to produce aryl ketones via visible-light-induced decarboxylative cross-coupling of α-oxocarboxylic acids and aryl boronic acids. This process was perfomed under air at room temperature,...

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