A general method for site-selective Csp3–S bond formation via cooperative catalysis

<div> <div> <div> <p>There are relatively few methods that accom- plish the selective alkoxylation of sp3-hybridized C–H bonds, particularly in comparison to the numerous analogous strate- gies for C–N and C–C bond formation. We report a photo- catalytic protocol for the functionalization of benzylic C–H bonds with a wide range of readily available oxygen nucleo- philes. Our strategy merges the photoredox activation of arenes with copper(II)-mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C–O bonds with high site selectivity, chemoselectivity, and functional group tolerance. This method enables the late- stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential appli- cations in synthesis and medicinal chemistry. </p> </div> </div> </div>

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Site-Selective Alkoxylation of Benzylic C–H Bonds via Photoredox Catalysis

10.26434/chemrxiv.8194226.v2 ◽

2019 ◽

Author(s):

Byung Joo Lee ◽

kimberly deglopper ◽

Tehshik Yoon

Keyword(s):

Late Stage ◽

Functional Group ◽

Bond Formation ◽

Bioactive Molecules ◽

Site Selectivity ◽

Wide Range ◽

High Site ◽

Alkoxy Groups ◽

Site Selective ◽

Mediated Oxidation

<div> <div> <div> <p>There are relatively few methods that accom- plish the selective alkoxylation of sp3-hybridized C–H bonds, particularly in comparison to the numerous analogous strate- gies for C–N and C–C bond formation. We report a photo- catalytic protocol for the functionalization of benzylic C–H bonds with a wide range of readily available oxygen nucleo- philes. Our strategy merges the photoredox activation of arenes with copper(II)-mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C–O bonds with high site selectivity, chemoselectivity, and functional group tolerance. This method enables the late- stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential appli- cations in synthesis and medicinal chemistry. </p> </div> </div> </div>

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Site-Selective Alkoxylation of Benzylic C–H Bonds via Photoredox Catalysis

10.26434/chemrxiv.8194226.v1 ◽

2019 ◽

Cited By ~ 2

Author(s):

Byung Joo Lee ◽

kimberly deglopper ◽

Tehshik Yoon

Keyword(s):

Late Stage ◽

Functional Group ◽

Bond Formation ◽

Bioactive Molecules ◽

Site Selectivity ◽

Wide Range ◽

High Site ◽

Alkoxy Groups ◽

Site Selective ◽

Mediated Oxidation

<div> <div> <div> <p>There are relatively few methods that accom- plish the selective alkoxylation of sp3-hybridized C–H bonds, particularly in comparison to the numerous analogous strate- gies for C–N and C–C bond formation. We report a photo- catalytic protocol for the functionalization of benzylic C–H bonds with a wide range of readily available oxygen nucleo- philes. Our strategy merges the photoredox activation of arenes with copper(II)-mediated oxidation of the resulting benzylic radicals, which enables the introduction of benzylic C–O bonds with high site selectivity, chemoselectivity, and functional group tolerance. This method enables the late- stage introduction of complex alkoxy groups into bioactive molecules, providing a practical new tool with potential appli- cations in synthesis and medicinal chemistry. </p> </div> </div> </div>

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Differentiation and Functionalization of Adjacent, Remote C–H Bonds

10.26434/chemrxiv.8156561 ◽

2019 ◽

Author(s):

Hang Shi ◽

Lu Yi ◽

Jiang Weng ◽

Katherine Bay ◽

Xiangyang Chen ◽

...

Keyword(s):

Catalytic System ◽

Functional Group ◽

Hydrocinnamic Acid ◽

Molecular Architectures ◽

Site Selective ◽

Developing Strategies

<p>Site-selective functionalizations of C–H bonds will ultimately afford chemists transformative tools for editing and constructing complex molecular architectures<sup>1-4</sup>. Towards this goal, developing strategies to activate C–H bonds that are distal from a functional group is essential<sup>4-6</sup>. In this context, distinguishing remote C–H bonds on adjacent carbon atoms is an extraordinary challenge due to the lack of electronic or steric bias between the two positions. Herein, we report the design of a catalytic system leveraging a remote directing template and a transient norbornene mediator to selectively activate a previously inaccessible remote C–H bond that is one bond further away. The generality of this approach has been demonstrated with a range of heterocycles, including a complex anti-leukemia agent, and hydrocinnamic acid substrates.</p>

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Modern Organic Synthesis in the Laboratory

10.1093/oso/9780195187984.001.0001 ◽

2008 ◽

Cited By ~ 1

Author(s):

Jie Jack Li ◽

Chris Limberakis ◽

Derek A. Pflum

Keyword(s):

Organic Chemistry ◽

Graduate Students ◽

Organic Synthesis ◽

Functional Group ◽

Bond Formation ◽

Reaction Conditions ◽

Carbon Bond ◽

Oxidation Reduction ◽

Carbon Carbon Bond ◽

Daunting Task

Searching for reaction in organic synthesis has been made much easier in the current age of computer databases. However, the dilemma now is which procedure one selects among the ocean of choices. Especially for novices in the laboratory, it becomes a daunting task to decide what reaction conditions to experiment with first in order to have the best chance of success. This collection intends to serve as an "older and wiser lab-mate" one could have by compiling many of the most commonly used experimental procedures in organic synthesis. With chapters that cover such topics as functional group manipulations, oxidation, reduction, and carbon-carbon bond formation, Modern Organic Synthesis in the Laboratory will be useful for both graduate students and professors in organic chemistry and medicinal chemists in the pharmaceutical and agrochemical industries.

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Recent Advances in C–Br Bond Formation

Synlett ◽

10.1055/s-0037-1610772 ◽

2021 ◽

Author(s):

Ying-Yeung Yeung ◽

Jonathan Wong

Keyword(s):

Organic Synthesis ◽

Aromatic Compounds ◽

Bond Formation ◽

Cross Coupling ◽

Catalytic Site ◽

Atom Transfer ◽

Bond Forming ◽

Recent Advances ◽

Catalytic Asymmetric ◽

Site Selective

AbstractOrganobromine compounds are extremely useful in organic synthesis. In this perspective, a focused discussion on some recent advancements in C–Br bond-forming reactions is presented.1 Introduction2 Selected Recent Advances2.1 Catalytic Asymmetric Bromopolycyclization of Olefinic Substrates2.2 Catalytic Asymmetric Intermolecular Bromination2.3 Some New Catalysts and Reagents for Bromination2.4 Catalytic Site-Selective Bromination of Aromatic Compounds2.5 sp3 C–H Bromination via Atom Transfer/Cross-Coupling3 Outlook

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A Site‐Selective C−N Bond Formation of 2,4‐Dichloro‐5 H ‐pyrano[2,3‐ d ]pyrimidines and Amide

ChemistrySelect ◽

10.1002/slct.202102824 ◽

2021 ◽

Vol 6 (43) ◽

pp. 12032-12035

Author(s):

Jinjing Qin ◽

Zhenhua Li ◽

Yingyan Cao ◽

Yuanyuan Xie ◽

Weike Su

Keyword(s):

Bond Formation ◽

A Site ◽

Site Selective

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Site-Selective C−S Bond Formation at C−Br over C−OTf and C−Cl Enabled by an Air-Stable, Easily Recoverable, and Recyclable Palladium(I) Catalyst

Angewandte Chemie International Edition ◽

10.1002/anie.201806036 ◽

2018 ◽

Vol 57 (38) ◽

pp. 12425-12429 ◽

Cited By ~ 37

Author(s):

Thomas Scattolin ◽

Erdem Senol ◽

Guoyin Yin ◽

Qianqian Guo ◽

Franziska Schoenebeck

Keyword(s):

Bond Formation ◽

Site Selective

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Copper-Catalyzed Intramolecular α-C–H Amination via Ring-Opening Cyclization Strategy to Quinazolin-4-ones: Development and Application in Rutaecarpine Synthesis

Synthesis ◽

10.1055/s-0037-1611575 ◽

2019 ◽

Vol 51 (16) ◽

pp. 3160-3170

Author(s):

Srilaxmi M. Patel ◽

Harika Chada ◽

Sonali Biswal ◽

Sonika Sharma ◽

Duddu S. Sharada

Keyword(s):

Ring Opening ◽

Functional Group ◽

Bond Cleavage ◽

Isatoic Anhydride ◽

General Method

A copper-catalyzed intramolecular α-C–H amination has been developed for the synthesis of quinazolin-4(3H)-one derivatives from commercially available isatoic anhydride and primary and secondary benzylamines via ring-opening cyclization (ROC). This method shows good functional group tolerance and allows access to a range of 2-aryl, 2-alkyl, and spiroquinazolinone derivatives. However, 2-methylquinazolin-4(3H)-one was synthesized from 2-amino-N-isopropylbenzamide by C–C bond cleavage, and N-benzyl-2-(methylamino)benzamide afforded 1-methyl-2-phenylquinazolin-4(1H)-one along with 2-phenylquinazolin-4(3H)-one by N–C bond cleavage for aromatization. It is the first general method to construct the potentially useful 2-methylquinazolin-4(3H)-one by copper-catalyzed intramolecular C–H amination. Also this ROC strategy has been successfully applied to the synthesis of quinazolinone alkaloid rutaecarpine.

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