scholarly journals Directed nickel-catalyzed regio- and diastereoselective arylamination of unactivated alkenes

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Leipeng Xie ◽  
Shenghao Wang ◽  
Lanlan Zhang ◽  
Lei Zhao ◽  
Chun Luo ◽  
...  
Keyword(s):  
Functional Group ◽  
Direct Access ◽  
Arylboronic Acids ◽  
Directing Group ◽  
Site Selective ◽  
Pharmaceutical Agents

AbstractFew methods have been reported for intermolecular arylamination of alkenes, which could provide direct access to important arylethylamine scaffolds. Herein, we report an intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitates formation of stabilized 4-, 5- or 6-membered nickelacycles and enables the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol is compatible with broad substrate scope and high functional group tolerance. The utility of this method is further demonstrated by the site-selective modification of pharmaceutical agents.

scholarly journals Nickel-Catalyzed Regio- and Diastereoselective Arylamination of Unactivated Alkenes

2021 ◽  
Author(s):  
Chao Wang ◽  
Shenghao Wang ◽  
Lanlan Zhang ◽  
Leipeng Xie ◽  
Lei Zhao ◽  
...  
Keyword(s):  
Late Stage ◽  
Functional Group ◽  
Arylboronic Acids ◽  
Directing Group ◽  
Site Selective ◽  
Pharmaceutical Agents

Abstract An intermolecular syn-1,2-arylamination of unactivated alkenes with arylboronic acids and O-benzoylhydroxylamine electrophiles has been developed with Ni(II) catalyst. The cleavable bidentate picolinamide directing group facilitated formation of stabilized 4-, 5- or 6-membered nickelacycles and enabled the difunctionalization of diverse alkenyl amines with high levels of regio-, chemo- and diastereocontrol. This general and practical protocol was compatible with broad substrate scope and high functional group tolerance. The utility of this method was further demonstrated by the site-selective late-stage modification of pharmaceutical agents.

scholarly journals A Transient Directing Group Strategy Enables Enantioselective Multicomponent Organofluorine Synthesis

2021 ◽  
Author(s):  
Zhonglin Liu ◽  
Lucas Oxtoby ◽  
Mingyu Liu ◽  
Zi-Qi Li ◽  
Van Tran ◽  
...  
Keyword(s):  
Bioactive Compounds ◽  
Arylboronic Acids ◽  
Group Strategy ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
Site Selective ◽  
Significant Attention ◽  
Three Component Coupling

The vicinal fluorofunctionalization of alkenes represents an expedient strategy for converting feedstock olefins into valuable fluorinated molecules and as such has garnered significant attention from the synthetic community; however, current methods remain limited in terms of scope and selectivity. Here we report the site-selective palladium-catalyzed three-component coupling of alkenylbenzaldehydes, arylboronic acids, and <i>N</i>-fluoro-2,4,6-trimethylpyridinium hexafluorophosphate facilitated by a transient directing group. The synthetically enabling methodology constructs vicinal stereocenters with excellent regio-, diastereo-, and enantioselectivities, forging products that map onto bioactive compounds.

scholarly journals A Transient Directing Group Strategy Enables Enantioselective Multicomponent Organofluorine Synthesis

2021 ◽  
Author(s):  
Zhonglin Liu ◽  
Lucas Oxtoby ◽  
Mingyu Liu ◽  
Zi-Qi Li ◽  
Van Tran ◽  
...  
Keyword(s):  
Bioactive Compounds ◽  
Arylboronic Acids ◽  
Group Strategy ◽  
Palladium Catalyzed ◽  
Directing Group ◽  
Site Selective ◽  
Significant Attention ◽  
Three Component Coupling

The vicinal fluorofunctionalization of alkenes represents an expedient strategy for converting feedstock olefins into valuable fluorinated molecules and as such has garnered significant attention from the synthetic community; however, current methods remain limited in terms of scope and selectivity. Here we report the site-selective palladium-catalyzed three-component coupling of alkenylbenzaldehydes, arylboronic acids, and <i>N</i>-fluoro-2,4,6-trimethylpyridinium hexafluorophosphate facilitated by a transient directing group. The synthetically enabling methodology constructs vicinal stereocenters with excellent regio-, diastereo-, and enantioselectivities, forging products that map onto bioactive compounds.

para-Selective Cyanation of Arenes by H-Bonded Template

2019 ◽  
Author(s):  
Sandeep Pimparkar ◽  
Trisha Bhattacharya ◽  
Arun Maji ◽  
Argha Saha ◽  
Ramasamy Jayarajan ◽  
...  
Keyword(s):  
Selective Functionalization ◽  
Directing Group ◽  
Product Utility ◽  
Site Selective

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the <i>para</i>-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of <i>para</i>-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications

para-Selective Cyanation of Arenes by H-Bonded Template

2019 ◽  
Author(s):  
Sandeep Pimparkar ◽  
Trisha Bhattacharya ◽  
Arun Maji ◽  
Argha Saha ◽  
Ramasamy Jayarajan ◽  
...  
Keyword(s):  
Selective Functionalization ◽  
Directing Group ◽  
Product Utility ◽  
Site Selective

The significance of site selective functionalization stands upon the superior selectivity, easy synthesis and diverse product utility. In this work we demonstrate the <i>para</i>-selective introduction of versatile nitrile moiety, enabled by detachable and reusable H-bonded auxiliary. The methodology holds its efficiency irrespective of substrate electronic bias. The conspicuous shift in the step energetics was probed by both experimental and computational mechanistic tools heralds the inception of <i>para</i>-deuteration. The synthetic impact of the methodology was highlighted with reusability of directing group and post synthetic modifications

Differentiation and Functionalization of Adjacent, Remote C–H Bonds

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>

scholarly journals Practical iridium-catalyzed direct α-arylation of N-heteroarenes with (hetero)arylboronic acids by H2O-mediated H2 evolution

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Liang Cao ◽  
He Zhao ◽  
Rongqing Guan ◽  
Huanfeng Jiang ◽  
Pierre. H. Dixneuf ◽  
...  
Keyword(s):  
Structural Modification ◽  
Universal Access ◽  
Boronic Acids ◽  
Direct Access ◽  
Bidentate Ligands ◽  
H2 Evolution ◽  
Arylboronic Acids ◽  
Coupling Strategy ◽  
General Method ◽  
Operational Simplicity

AbstractDespite the widespread applications of 2-(hetero)aryl N-heteroarenes in numerous fields of science and technology, universal access to such compounds is hampered due to the lack of a general method for their synthesis. Herein, by a H2O-mediated H2-evolution cross-coupling strategy, we report an iridium(III)-catalyzed facile method to direct α-arylation of N-heteroarenes with both aryl and heteroaryl boronic acids, proceeding with broad substrate scope and excellent functional compatibility, oxidant and reductant-free conditions, operational simplicity, easy scalability, and no need for prefunctionalization of N-heteroarenes. This method is applicable for structural modification of biomedical molecules, and offers a practical route for direct access to 2-(hetero)aryl N-heteroarenes, a class of potential cyclometalated C^N ligands and N^N bidentate ligands that are difficult to prepare with the existing α-C-H arylation methods, thus filling an important gap in the capabilities of synthetic organic chemistry.

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

2020 ◽  
Vol 11 (5) ◽  
pp. 1276-1282 ◽  
Author(s):  
Yuman Qin ◽  
Yujie Han ◽  
Yongzhen Tang ◽  
Junfa Wei ◽  
Mingyu Yang
Keyword(s):  
Functional Group ◽  
Bond Formation ◽  
Aliphatic Amines ◽  
Cooperative Catalysis ◽  
Site Selective ◽  
General Method

A copper-catalyzed site-selective thiolation of Csp3–H bonds of aliphatic amines was developed. The method features a broad substrate scope and good functional group tolerance.

scholarly journals A lesson for site-selective C–H functionalization on 2-pyridones: radical, organometallic, directing group and steric controls

2018 ◽  
Vol 9 (1) ◽  
pp. 22-32 ◽  
Author(s):  
Koji Hirano ◽  
Masahiro Miura
Keyword(s):  
Pharmaceutical Chemistry ◽  
Recent Advances ◽  
Directing Group ◽  
Site Selective

This minireview focuses on recent advances in site-selective C–H functionalization on 2-pyridone which is an important heterocyclic motif in medicinal and pharmaceutical chemistry.

Visible-Light-Induced Radical Polynitration of Arylboronic Acids: Synthesis of Polynitrophenols

Synthesis ◽  
2018 ◽  
Vol 50 (15) ◽  
pp. 2891-2896 ◽  
Author(s):  
Jinna Song ◽  
Xihe Bi ◽  
Qi Zhang ◽  
Kaki Raveendra Babu ◽  
Zhouliang Huang
Keyword(s):  
Visible Light ◽  
Aromatic Compounds ◽  
Functional Group ◽  
Simple Procedure ◽  
One Pot ◽  
Arylboronic Acids ◽  
Mild Conditions ◽  
Conventional Methods ◽  
Straightforward Approach

We report a visible light-assisted one-pot method for the synthesis of polynitrophenols through radical tandem hydroxylation and nitration of arylboronic acids by utilizing copper(II) nitrate tri­hydrate as the nitro source. This method features mild conditions, a simple procedure, and good functional group tolerance. Compared to conventional methods, this work provides a straightforward approach for the polynitration of aromatic compounds.

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