Copper-Catalyzed Hydrocarboxylation of Allenes

2019 ◽  
Author(s):  
Rémi blieck ◽  
Marc Taillefer ◽  
Florian Monnier
Keyword(s):  
Carboxylic Acids ◽  
Copper Catalysis ◽  
Ligand Free ◽  
First Time

The addition of carboxylic acids to allenes was performed for the first time with copper catalysis. The hydrocarboxylation reaction is totally regio- and stereoselective, ligand-free and used catalytic amounts of copper and base.

Copper-Catalyzed Hydrocarboxylation of Allenes

2019 ◽  
Author(s):  
Rémi blieck ◽  
Marc Taillefer ◽  
Florian Monnier
Keyword(s):  
Carboxylic Acids ◽  
Copper Catalysis ◽  
Ligand Free ◽  
First Time

The addition of carboxylic acids to allenes was performed for the first time with copper catalysis. The hydrocarboxylation reaction is totally regio- and stereoselective, ligand-free and used catalytic amounts of copper and base.

ChemInform Abstract: “Ligand-Free” Palladium-Catalyzed Direct C-H Bond Oxidative Acyloxylation of 2-Arylpyridines with Aromatic Carboxylic Acids.

ChemInform ◽  
2012 ◽  
Vol 43 (35) ◽  
pp. no-no
Author(s):  
Chao-Jun Hu ◽  
Xiao-Hong Zhang ◽  
Qiu-Ping Ding ◽  
Ting Lv ◽  
Shao-Peng Ge ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Aromatic Carboxylic Acids ◽  
Ligand Free ◽  
Palladium Catalyzed

scholarly journals Late-Stage β-C(sp3)–H Deuteration of Carboxylic Acids

2021 ◽  
Author(s):  
Alexander Uttry ◽  
Sourjya Mal ◽  
Manuel van Gemmeren
Keyword(s):  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Late Stage ◽  
Bioactive Molecules ◽  
Wide Range ◽  
Catalyst Systems ◽  
First Time

Carboxylic acid moieties are highly abundant in bioactive molecules. In this study we describe the late-stage β-C(sp<sup>3</sup>)–H deuteration of free carboxylic acids. Based on our finding that the C–H activation with our catalyst systems is reversible, the de-deuteration process was first optimized. The resulting conditions involve ethylenediamine-based ligands, which, amongst other positions, for the first time enables the functionalization of non-activated methylene β-C(sp<sup>3</sup>)–H bonds and can be used to achieve the desired deuteration when using a deuterated solvent. The reported method allows for the functionalization of a wide range of free carboxylic acids with diverse substitution patterns, as well as the late-stage deuteration of bioactive molecules and related frameworks.

Azo-Compound-Mediated Cyanoalkylation of Alkenes by Copper Catalysis: General Access to Cyano-Substituted Oxindoles

Synthesis ◽  
2015 ◽  
Vol 47 (11) ◽  
pp. 1567-1580 ◽  
Author(s):  
Shi Tang ◽  
Dong Zhou ◽  
Zhi-Hao Li ◽  
Mei-Jun Fu ◽  
Li Jie ◽  
...  
Keyword(s):  
Radical Addition ◽  
Copper Catalysis ◽  
Azo Compound ◽  
Highly Efficient ◽  
First Time ◽  
General Synthesis

A practical and highly efficient azo-compound-mediated/ promoted radical cyanoalkylation of activated alkenes by copper catalysis was developed, which allowed for general synthesis of oxindoles bearing various nitrile moieties, especially the rarely reported 3° nitrile moiety via cascade radical addition/C(sp2)–H cyclization. This protocol demonstrates that DIAD served for a new promoter instead of usual Ag salts or bases in the C(sp3)–H functionalization of acetonitrile for the first time. The use of readily available AIBN and beyond as the radical sources, and inexpensive copper as the catalyst, as well as the simplicity of operation and handling, make this protocol an attractive access to therapeutically important cyano-substituted oxindoles.

Oxido-molybdenum complexes obtained by Cl/O interchange between MoCl5 and carboxylic acids: a crystallographic, spectroscopic and computational study

2014 ◽  
Vol 43 (43) ◽  
pp. 16416-16423 ◽  
Author(s):  
Marco Bortoluzzi ◽  
Fabio Marchetti ◽  
Guido Pampaloni ◽  
Stefano Zacchini
Keyword(s):  
Carboxylic Acids ◽  
Computational Study ◽  
Molybdenum Complexes ◽  
First Time

The reactivity of MoCl5 with carboxylic acids has been elucidated for the first time. The reactions are featured by the chlorinating behaviour of MoCl5, rather than affording the respective carboxylato complexes.

ChemInform Abstract: Ligand-Free Pd-Catalyzed Decarboxylative Arylation of Imidazo[1,2-a]pyridine-3-carboxylic Acids with Aryl Bromides.

ChemInform ◽  
2016 ◽  
Vol 47 (48) ◽  
Author(s):  
Uttam B. Karale ◽  
Saradhi Kalari ◽  
Jala Shivakumar ◽  
Vitthal B. Makane ◽  
Dattatraya A. Babar ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Aryl Bromides ◽  
Ligand Free

scholarly journals First Crystal Structure of Bacterial Oligopeptidase B in an Intermediate State: The Roles of the Hinge Region Modification and Spermine

Biology ◽  
2021 ◽  
Vol 10 (10) ◽  
pp. 1021
Author(s):  
Dmitry E. Petrenko ◽  
Vladimir I. Timofeev ◽  
Vladimir V. Britikov ◽  
Elena V. Britikova ◽  
Sergey Y. Kleymenov ◽  
...  
Keyword(s):  
Intermediate State ◽  
Conformational Transition ◽  
Dynamic Equilibrium ◽  
Catalytic Triad ◽  
Hinge Region ◽  
Wild Type ◽  
Oligopeptidase B ◽  
Ligand Free ◽  
Key Factor ◽  
First Time

Oligopeptidase B (OpB) is a two-domain, trypsin-like serine peptidase belonging to the S9 prolyloligopeptidase (POP) family. Two domains are linked by a hinge region that participates in the transition of the enzyme between two major states—closed and open—in which domains and residues of the catalytic triad are located close to each other and separated, respectively. In this study, we described, for the first time, a structure of OpB from bacteria obtained for an enzyme from Serratia proteomaculans with a modified hinge region (PSPmod). PSPmod was crystallized in a conformation characterized by a disruption of the catalytic triad together with a domain arrangement intermediate between open and closed states found in crystals of ligand-free and inhibitor-bound POP, respectively. Two additional derivatives of PSPmod were crystallized in the same conformation. Neither wild-type PSP nor its corresponding mutated variants were susceptible to crystallization, indicating that the hinge region modification was key in the crystallization process. The second key factor was suggested to be polyamine spermine since all crystals were grown in its presence. The influences of the hinge region modification and spermine on the conformational state of PSP in solution were evaluated by small-angle X-ray scattering. SAXS showed that, in solution, wild-type PSP adopted the open state, spermine caused the conformational transition to the intermediate state, and spermine-free PSPmod contained molecules in the open and intermediate conformations in dynamic equilibrium.

scholarly journals Stereospecific, Ligand-Free Synthesis of All-Carbon Quaternary Stereocenters from Tertiary Benzylic Carboxylates

2021 ◽  
Author(s):  
Jianyu Xu ◽  
Sarah Pound ◽  
Corey Basch ◽  
Alana Duke ◽  
Mary Watson
Keyword(s):  
The Past ◽  
Ligand Free ◽  
Quaternary Stereocenters ◽  
High Yields ◽  
First Time

Nickel-catalyzed, stereospecific cross-couplings via activation of secondary C–O bonds has been well developed in the past few years. Meanwhile, stereospecific cross-couplings of tertiary electrophiles have been rarely explored. Herein, we describe a nickel-catalyzed, ligand-free Suzuki-Miyaura vinylation, using easily prepared, highly enantioenriched tertiary benzylic carboxylates to install all-carbon quaternary stereocenters in high yields and ee’s. In addition to allowing stereospecific vinylation of these substrates for the first time, this method overcomes the longstanding requirement for a naphthyl group on the benzylic carboxylate<br>

scholarly journals Ligand-Controlled Regiodivergence in Nickel-Catalyzed Hydroarylation and Hydroalkenylation of Alkenyl Carboxylic Acids

2020 ◽  
Author(s):  
Zi-Qi Li ◽  
Yue Fu ◽  
Ruohan Deng ◽  
Van Tran ◽  
Yang Gao ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Transition State ◽  
Carboxylic Acids ◽  
Alkyl Group ◽  
Steric Effects ◽  
High Yield ◽  
Mechanistic Studies ◽  
Ligand Environment ◽  
Ligand Free ◽  
Electronic And Steric Effects

<div>A nickel-catalyzed regiodivergent hydroarylation and hydroalkenylation of unactivated alkenyl carboxylic acids is reported, whereby the ligand environment around the metal center dictates the regiochemical outcome. Markovnikov hydrofunctionalization products are obtained under mild ligand-free conditions, with up to 99% yield and >20:1 selectivity. Alternatively, anti-Markovnikov products can be accessed with a novel 4,4-disubstituted Pyrox ligand in excellent yield and >20:1 selectivity. Both electronic and steric effects on the ligand contribute to the high yield and selectivity. Mechanistic studies suggest a change in the turnover-limiting and selectivity-determining step induced by the optimal ligand. DFT calculations reveal that in the anti-Markovnikov pathway, repulsion between the ligand and the alkyl group is minimized (by virtue of it being 1° versus 2°) in the rate- and regioselectivity-determining transmetalation transition state. <br></div>

A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for aerobic oxidation of alcohols

2020 ◽  
Vol 56 (82) ◽  
pp. 12443-12446
Author(s):  
Xianjin Zhu ◽  
Can Liu ◽  
Yong Liu ◽  
Haijun Yang ◽  
Hua Fu
Keyword(s):  
Carboxylic Acids ◽  
Aerobic Oxidation ◽  
Primary Alcohols ◽  
Oxidation Of Alcohols ◽  
First Time

A sodium trifluoromethanesulfinate-mediated photocatalytic strategy for the aerobic oxidation of secondary and primary alcohols to ketones and carboxylic acids has been developed for the first time.

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