Chemoselective sp3-C–H Activation in Oxidative Coupling to Form Quaternary Centers

Synfacts ◽  
2019 ◽  
Vol 15 (06) ◽  
pp. 0624
Keyword(s):  
Oxidative Coupling ◽  
Quaternary Centers

scholarly journals Palladium-Catalyzed Chemoselective Activation of sp3 vs sp2 C–H Bonds: Oxidative Coupling To Form Quaternary Centers

ACS Catalysis ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 3716-3724 ◽  
Author(s):  
Gang Hong ◽  
Pradip D. Nahide ◽  
Uday Kumar Neelam ◽  
Peter Amadeo ◽  
Arjun Vijeta ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Quaternary Centers ◽  
Palladium Catalyzed

Diastereoselective construction of continuous all-carbon quaternary centers via intramolecular oxidative coupling reaction

2013 ◽  
Vol 54 (33) ◽  
pp. 4392-4396 ◽  
Author(s):  
Weiqing Xie ◽  
Hexiang Wang ◽  
Feng Fan ◽  
Junshan Tian ◽  
Zhiwei Zuo ◽  
...  
Keyword(s):  
Oxidative Coupling ◽  
Coupling Reaction ◽  
Quaternary Centers ◽  
Oxidative Coupling Reaction

Metal-Free Photoinduced Hydroalkylation Cascade Enabled by an Electron-Donor-Acceptor Complex

2020 ◽  
Author(s):  
José Tiago Menezes Correia ◽  
Gustavo Piva da Silva ◽  
Camila Menezes Kisukuri ◽  
Elias André ◽  
Bruno Pires ◽  
...  
Keyword(s):  
Electron Donor ◽  
Functional Group ◽  
Photoexcited Electron ◽  
One Pot ◽  
Quaternary Centers ◽  
Metal Free ◽  
Acceptor Complex ◽  
Catalyst Free ◽  
Donor Acceptor ◽  
Radical Cascade

A metal- and catalyst-free photoinduced radical cascade hydroalkylation of 1,7-enynes has been disclosed. The process is triggered by a SET event involving a photoexcited electron-donor-aceptor complex between NHPI ester and Hantzsch ester, which decomposes to afford a tertiary radical that is readily trapped by the enyne. <a>The method provides an operationally simple, robust and step-economical approach to the construction of diversely functionalized dihydroquinolinones bearing quaternary-centers. A sequential one-pot hydroalkylation-isomerization approach is also allowed giving access to a family of quinolinones. A wide substrate scope and high functional group tolerance was observed in both approaches</a>.

Diverse Cyclopentenes via Enantioselective Cu-Catalyzed Desymmetrization

2018 ◽  
Author(s):  
Reece Jacques ◽  
Robert D. C. Pullin ◽  
Stephen P. Fletcher
Keyword(s):  
Ring Systems ◽  
Quaternary Centers ◽  
Stereogenic Centers

<div> <div> <div> <p>A highly regio-, diastereo- and enantioselective Cu-catalyzed desymmetrization of diverse meso-bisphosphates with alkyl zirconium nucleophiles has been developed. The reaction allows access to a broad range of functionalized cyclopentenes with up to three contiguous stereogenic centers, including quaternary centers and spirocyclic ring systems.</p></div></div></div>

Diverse Cyclopentenes via Enantioselective Cu-Catalyzed Desymmetrization

2018 ◽  
Author(s):  
Reece Jacques ◽  
Robert D. C. Pullin ◽  
Stephen P. Fletcher
Keyword(s):  
Ring Systems ◽  
Quaternary Centers ◽  
Stereogenic Centers

<div> <div> <div> <p>A highly regio-, diastereo- and enantioselective Cu-catalyzed desymmetrization of diverse meso-bisphosphates with alkyl zirconium nucleophiles has been developed. The reaction allows access to a broad range of functionalized cyclopentenes with up to three contiguous stereogenic centers, including quaternary centers and spirocyclic ring systems.</p></div></div></div>

Synthesis of Nitrile-Bearing Quaternary Centers via an Equilibrium-Driven Transnitrilation and Anion-Relay Strategy

2019 ◽  
Author(s):  
Sebastien Alazet ◽  
Michael West ◽  
Purvish Patel ◽  
Sophie Rousseaux
Keyword(s):  
Building Blocks ◽  
One Pot ◽  
Quaternary Centers ◽  
Synthetic Intermediates

The efficient preparation of nitrile-containing building blocks is of interest due to their utility as synthetic intermediates and their prevalence in pharmaceuticals. As a result, significant efforts have been made to develop methods to access these motifs which rely on safer and non-toxic sources of CN. Herein, we report that 2-methyl-2-phenylpropanenitrile is an efficient, non-toxic, electrophilic CN source for the synthesis of nitrile-bearing quaternary centers via a thermodynamic transnitrilation and anion-relay strategy. This one-pot process leads to nitrile products resulting from the gem-difunctionalization of alkyl lithium reagents.<br>

An Unprecedented Cyano-Induced Sodium Nitrite-Catalyzed C(sp3)-H and C(sp2)-H Coupling Reaction

2018 ◽  
Vol 15 (7) ◽  
pp. 989-994 ◽  
Author(s):  
Ling Li ◽  
Bo Su ◽  
Yuxiu Liu ◽  
Qingmin Wang
Keyword(s):  
Sodium Nitrite ◽  
Oxidative Coupling ◽  
High Resolution Mass Spectrometry ◽  
Coupling Reaction ◽  
13C Nmr Spectroscopy ◽  
Coupling Reactions ◽  
Reaction Conditions ◽  
1H And 13C Nmr ◽  
Oxidative Coupling Reaction ◽  
Oxidative Coupling Reactions

Aim and Objective: During the investigation of sodium nitrite-catalyzed oxidative coupling reaction of aryls, an unprecedented C(sp2)-H and C(sp3)-H coupling of substituted 2-aryl acetonitrile was found. Materials and Methods: The structure of the coupled product was confirmed by 1H and 13C NMR spectroscopy and high-resolution mass spectrometry (HRMS), and comparison of its derivatives with known compounds. The effects of methoxy group in the benzene ring on the reaction were evaluated. Results: The optimized reaction conditions are summarized as follows: CF3SO3H/substrate = 1.5 equiv., NaNO2/substrate = 0.3 equiv., CH3CN as solvent. 2-(4-Methoxyphenyl)acetonitrile and 2-(3,4,5- trimethoxyphenyl)acetonitrile could also generate C(sp2)-H and C(sp3)-H coupling. The coupling reaction occurred as a typical radial mechanism. Conclusion: An unprecedented cyano-induced, NaNO2-catalyzed oxidative C(sp3)-H and C(sp2)-H coupling was reported. The reaction proceeded under very mild conditions, using O2 in the air as terminal oxidant. The unique oxidative manner might provide more inspiration for the development of intriguing oxidative coupling reactions.

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