scholarly journals An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

2020 ◽  
Author(s):  
Lingxiang Lu ◽  
Juno Siu ◽  
Yihuan Lai ◽  
Song Lin
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Reductive Cleavage ◽  
Materials Chemistry ◽  
Metal Free ◽  
Silyl Radical ◽  
Silyl Radicals ◽  
New Strategy ◽  
Radical Generation ◽  
Synthetic Medicinal

The construction of C(sp<sup>3</sup>)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

scholarly journals An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

2020 ◽  
Author(s):  
Lingxiang Lu ◽  
Juno Siu ◽  
Yihuan Lai ◽  
Song Lin
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Reductive Cleavage ◽  
Materials Chemistry ◽  
Metal Free ◽  
Silyl Radical ◽  
Silyl Radicals ◽  
New Strategy ◽  
Radical Generation ◽  
Synthetic Medicinal

The construction of C(sp<sup>3</sup>)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

scholarly journals An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

2020 ◽  
Author(s):  
Lingxiang Lu ◽  
Juno Siu ◽  
Yihuan Lai ◽  
Song Lin
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Reductive Cleavage ◽  
Materials Chemistry ◽  
Metal Free ◽  
Silyl Radical ◽  
Silyl Radicals ◽  
New Strategy ◽  
Radical Generation ◽  
Synthetic Medicinal

The construction of C(sp<sup>3</sup>)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

scholarly journals An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

2020 ◽  
Author(s):  
Lingxiang Lu ◽  
Juno Siu ◽  
Yihuan Lai ◽  
Song Lin
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Reductive Cleavage ◽  
Materials Chemistry ◽  
Metal Free ◽  
Silyl Radical ◽  
Silyl Radicals ◽  
New Strategy ◽  
Radical Generation ◽  
Synthetic Medicinal

The construction of C(sp<sup>3</sup>)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

Carbon Dioxide-Mediated C(sp2)–H Arylation of Primary and Secondary Benzylamines

2018 ◽  
Author(s):  
Mohit Kapoor ◽  
Pratibha Chand-Thakuri ◽  
Michael Young
Keyword(s):  
Carbon Dioxide ◽  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Carbon Bond ◽  
Chelate Effect ◽  
Free Amine ◽  
Carbon Carbon Bond ◽  
New Strategy ◽  
Metal Catalyzed

Carbon-carbon bond formation by transition metal-catalyzed C–H activation has become an important strategy to fabricate new bonds in a rapid fashion. Despite the pharmacological importance of <i>ortho</i>-arylbenzylamines, however, effective <i>ortho</i>-C–C bond formation from C–H bond activation of free primary and secondary benzylamines using Pd<sup>II</sup> remains an outstanding challenge. Presented herein is a new strategy for constructing <i>ortho</i>-arylated primary and secondary benzylamines mediated by carbon dioxide (CO<sub>2</sub>). The use of CO<sub>2</sub> is critical to allowing this transformation to proceed under milder conditions than previously reported, and that are necessary to furnish free amine products that can be directly used or elaborated without the need for deprotection. In cases where diarylation is possible, a chelate effect is demonstrated to facilitate selective monoarylation.

Facile Access to Triazole-Fused 3,1-Benzoxazines Enabled by Metal-Free Base-Promoted Intramolecular C–O Coupling

Synthesis ◽  
2021 ◽  
Author(s):  
Yury N. Kotovshchikov ◽  
Stepan S. Tatevosyan ◽  
Gennadij V. Latyshev ◽  
Nikolay V. Lukashev ◽  
Irina P. Beletskaya
Keyword(s):  
Transition Metal ◽  
Functional Group ◽  
Cost Effective ◽  
Reductive Cleavage ◽  
Effective Procedure ◽  
Free Base ◽  
Metal Free ◽  
Fused Heterocycles ◽  
Convenient Approach

AbstractA convenient approach to assemble 1,2,3-triazole-fused 4H-3,1-benzoxazines has been developed. Diverse alcohol-tethered 5-iodotriazoles, readily accessible by a modified protocol of Cu-catalyzed (3+2)-cycloaddition, were utilized as precursors of the target fused heterocycles. The intramolecular C–O coupling proceeded efficiently under base-mediated transition-metal-free conditions, furnishing cyclization products in yields up to 96%. Suppression of the competing reductive cleavage of the C–I bond was achieved by the use of Na2CO3 in acetonitrile at 100 °C. This practical and cost-effective procedure features a broad substrate scope and valuable functional group tolerance.

Hydride-catalyzed selectively reductive cleavage of unactivated tertiary amides using hydrosilane

2019 ◽  
Vol 9 (15) ◽  
pp. 3874-3878 ◽  
Author(s):  
Wubing Yao ◽  
Rongrong Li ◽  
Jianguo Yang ◽  
Feiyue Hao
Keyword(s):  
Transition Metal ◽  
Reductive Cleavage ◽  
Metal Free ◽  
Free Process ◽  
Tertiary Amides ◽  
Current Systems

The first hydride-catalyzed reductive cleavage of tertiary amides using the hydrosilane as reducing reagent has been developed. This transition-metal-free process may offer a versatile alternative to current systems for the selective reductive cleavage of amides.

Non-Classical Amide Bond Formation: Transamidation and Amidation of Activated Amides and Esters by Selective N–C/O–C Cleavage

Synthesis ◽  
2020 ◽  
Vol 52 (18) ◽  
pp. 2579-2599 ◽  
Author(s):  
Michal Szostak ◽  
Guangchen Li
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Bond Formation ◽  
Amide Bond ◽  
Acyl Transfer ◽  
Metal Free ◽  
Amide Bond Formation ◽  
New Methods ◽  
Formidable Challenge ◽  
Tetrahedral Intermediates

In the past several years, tremendous advances have been made in non-classical routes for amide bond formation that involve transamidation and amidation reactions of activated amides and esters. These new methods enable the formation of extremely valuable amide bonds via transition-metal-catalyzed, transition-metal-free, or metal-free pathways by exploiting chemoselective acyl C–X (X = N, O) cleavage under mild conditions. In a broadest sense, these reactions overcome the formidable challenge of activating C–N/C–O bonds of amides or esters by rationally tackling nN → π*C=O delocalization in amides and nO → π*C=O donation in esters. In this account, we summarize the recent remarkable advances in the development of new methods for the synthesis of amides with a focus on (1) transition-metal/NHC-catalyzed C–N/C–O bond activation, (2) transition-metal-free highly selective cleavage of C–N/C–O bonds, (3) the development of new acyl-transfer reagents, and (4) other emerging methods.1 Introduction2 Transamidation of Amides2.1 Transamidation by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)2.2 Transition-Metal-Free Transamidation via Tetrahedral Intermediates2.3 Reductive Transamidation2.4 New Acyl-Transfer Reagents2.5 Tandem Transamidations3 Amidation of Esters3.1 Amidation of Esters by Metal–NHC Catalysis (Pd–NHC, Ni–NHC)3.2 Transition-Metal-Free Amidation of Esters via Tetrahedral Intermediates3.3 Reductive Amidation of Esters4 Transamidations of Amides by Other Mechanisms5 Conclusions and Outlook

Transition-metal-free site-selective C–F bond activation for synthesis of 8-aminoquinolines

2017 ◽  
Vol 58 (45) ◽  
pp. 4240-4242 ◽  
Author(s):  
Jianping Chen ◽  
Dongyang Huang ◽  
Yuqiang Ding
Keyword(s):  
Transition Metal ◽  
Bond Activation ◽  
Metal Free ◽  
Site Selective

Transition-metal-free decarboxylation of dimethyl malonate: an efficient construction of α-amino acid esters using TBAI/TBHP

2015 ◽  
Vol 13 (13) ◽  
pp. 3982-3987 ◽  
Author(s):  
Jie Zhang ◽  
Ying Shao ◽  
Yaxiong Wang ◽  
Huihuang Li ◽  
Dongmei Xu ◽  
...  
Keyword(s):  
Amino Acid ◽  
Transition Metal ◽  
Nucleophilic Substitution ◽  
Amino Acid Esters ◽  
Dimethyl Malonate ◽  
Metal Free ◽  
New Strategy ◽  
Efficient Construction ◽  
Acid Esters

A new strategy has been developed for the synthesis of α-amino acid esters via a tandem hydrolysis/decarboxylation/nucleophilic substitution using TBAI/TBHP.

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