scholarly journals N-Tosylcarboxamide in C–H Functionalization: More than a Simple Directing Group

Processes ◽  
2020 ◽  
Vol 8 (8) ◽  
pp. 981
Author(s):  
Benjamin Large ◽  
Vincent Terrasson ◽  
Damien Prim
Keyword(s):  
Transition Metal ◽  
Functional Groups ◽  
Organic Synthesis ◽  
Transition Metal Catalysis ◽  
Ortho Position ◽  
Aromatic Rings ◽  
One Pot ◽  
Complex Molecules ◽  
Metal Catalysis ◽  
Directing Group

C–H activation with transition metal catalysis has become an important tool in organic synthesis for the functionalization of low reactive bonds and the preparation of complex molecules. The choice of the directing group (DG) proves to be crucial for the selectivity in this type of reaction, and several different functional groups have been used efficiently. This review describes recent advances in C–H functionalization of aromatic rings directed by a N-tosylcarboxamide group. Results regarding alkenylation, alkoxylation, halogenation, and arylation of C–H in the ortho position to the tosylcarboxamide are presented. Moreover, the advantage of this particular directing group is that it can undergo further transformation and act as CO or CON fragment reservoir to produce, in sequential fashion or one-pot sequence, various interesting (hetero)cycles such as phenanthridinones, dihydroisoquinolinones, fluorenones, or isoindolinones.

scholarly journals Unsymmetrical Difunctionalization of Two Different C–H Bonds in One Pot Under Transition-Metal Catalysis

Synthesis ◽  
2018 ◽  
Vol 51 (01) ◽  
pp. 40-54 ◽  
Author(s):  
Masahito Murai ◽  
Kazuhiko Takai
Keyword(s):  
Transition Metal ◽  
Functional Groups ◽  
Aromatic Compounds ◽  
Transition Metal Catalysis ◽  
One Pot ◽  
Metal Catalysis ◽  
Selective Functionalization ◽  
Sequential Addition ◽  
Target Molecules ◽  
Directing Group

Recent advancements in unsymmetrical difunctionalization based on the substitution of two different C–H bonds in one-pot are described. Due to the difficulty of controlling reactivity and selectivity, multi-functionalization via substitution of several C–H bonds to install different functional groups has been limited until recently, in comparison with well-studied functionalization via sequential addition to unsaturated π-bonds. This difunctionalization protocol provides an efficient and rapid approach to a library of structurally complicated target molecules through the formation of multiple C–X bonds with high atom- and step-economy.1 Introduction2 ortho-Selective Functionalization of Two Different C–H Bonds Relative to the Directing Group2.1 Unsymmetrical Difunctionalization with the Introduction of Similar Functional Groups2.2 Unsymmetrical Difunctionalization with the Introduction of Different Functional Groups2.3 ortho-Selective Unsymmetrical Difunctionalization Promoted by Two Different Directing Groups Appearing During the Progress of the Reaction3 ortho/meta-Selective C–H Bond Difunctionalization Relative to the Directing Group4 Sequential Difunctionalization of Fused Aromatic Compounds and Heterocycles5 Summary and Outlook

An electrochemical perspective on the roles of ligands in the merger of transition-metal catalysis and electrochemistry

2020 ◽  
Author(s):  
Ke-Yin Ye ◽  
Jun-Song Zhong ◽  
Yi Yu ◽  
Zhaojiang Shi
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Transition Metal Catalysis ◽  
Metal Catalysis

The merger of transition-metal catalysis and electrochemistry has been emerging as a very versatile and robust synthetic tool in organic synthesis. Like in their non-electrochemical variants, ligands also play crucial...

Transition metal catalysis in organic synthesis: reflections, chirality and new vistas

1999 ◽  
Vol 71 (8) ◽  
pp. 1425-1433 ◽  
Author(s):  
Pavel Kočovský ◽  
Andrei V. Malkov ◽  
Štěpán Vyskočil ◽  
Guy C. Lloyd-Jones
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Transition Metal Catalysis ◽  
Metal Catalysis

scholarly journals Sulfoxonium Ylide Derived Metal Carbenoids in Organic Synthesis

Synthesis ◽  
2018 ◽  
Vol 51 (03) ◽  
pp. 612-628 ◽  
Author(s):  
Janakiram Vaitla ◽  
Annette Bayer
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Transition Metal Catalysis ◽  
Transfer Reactions ◽  
Reaction Conditions ◽  
Widespread Application ◽  
Metal Catalysis ◽  
Half Century ◽  
Metal Carbenoids

As pioneered by Corey and Chaykovsky, sulfoxonium ylides have had widespread application in organic synthesis for more than a half century. In most of the reactions, sulfoxonium ylides were used to react with electrophiles. Under suitable reaction conditions these ylides can generate metal carbenoids and react with nucleophiles. By combining the typical reactivity of sulfoxonium ylides with transition-metal catalysis, a growing number of investigations have expanded their application in organic synthesis. This review provides an update on the preparation of sulfoxonium ylides and their applications in carbenoid transfer reactions.1 Introduction2 Preparation of Sulfoxonium Ylides3 Investigation for Carbenoid Formation from Sulfoxonium Ylide 4 X–H (X = N, O, S, C) Functionalization Reactions5 Polymerizaton of Carbenoids Generated from Sulfoxonium Ylides6 Conclusion and Perspective

Thieme Chemistry Journals Awardees – Where Are They Now? New Reaction Mode in Carboxylate-Directed C–H Functionalizations: Carboxylates as Deciduous Directing Groups

Synlett ◽  
2017 ◽  
Vol 28 (15) ◽  
pp. 1885-1890 ◽  
Author(s):  
Lukas Gooßen ◽  
Agostino Biafora
Keyword(s):  
Transition Metal ◽  
Carboxylic Acids ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Carboxylate Groups ◽  
Specific Position ◽  
Directing Group ◽  
Leaving Groups ◽  
Unique Potential

The widely available carboxylate groups have recently emerged as advantageous leaving groups for regioselective ipso substitutions and directing groups for ortho-C–H functionalizations in transition-metal catalysis. In the latter reactions, they can subsequently be transformed into a wealth of functionalities through decarboxylative ipso substitutions, or tracelessly removed through protodecarboxylation. The latest development in this field are reactions in which carboxylic acids function as deciduous directing groups, unlocking their unique potential for achieving regioselective monofunctionalization of a single ortho-C–H position. A deciduous directing group stays in place just long enough to direct an incoming reagent into a specific position and is then shed tracelessly as soon as the new C–C or C–heteroatom bond has formed. This inherently prevents unwanted double functionalization. This account discusses characteristics and synthetic opportunities of reactions with carboxylates as deciduous directing groups.

Sono-Transition-Metal Catalysis of One-Pot Three-Step Synthesis of Glycosyl-1,2,3-triazoles

2013 ◽  
Vol 43 (13) ◽  
pp. 1808-1817 ◽  
Author(s):  
Mohsine Driowya ◽  
Khalid Bougrin ◽  
Rachid Benhida
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
One Pot ◽  
Metal Catalysis

Metallaphotoredox Catalysis for Multicomponent Coupling Reactions

2021 ◽  
Author(s):  
Wen-Jing Xiao ◽  
Fu-Dong Lu ◽  
Gui-Feng He ◽  
Liang-Qiu Lu
Keyword(s):  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Coupling Reactions ◽  
Complex Molecules ◽  
Metal Catalysis ◽  
Mild Conditions ◽  
Multicomponent Coupling Reactions ◽  
Multicomponent Coupling

The combination of photoredox and transition metal catalysis, which is termed metallaphotoredox catalysis, is a powerful platform for building complex molecules under mild conditions. In particular, metallaphotoredox-catalyzed multicomponent coupling reactions,...

Quasi-nature catalysis. Rhodium-catalyzed C­C bond formation in air and water

2001 ◽  
Vol 73 (8) ◽  
pp. 1315-1318 ◽  
Author(s):  
Taisheng Huang ◽  
Sripathy Venkatraman ◽  
Yue Meng ◽  
Tien V. Nguyen ◽  
Daniel Kort ◽  
...  
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Bond Formation ◽  
Transition Metal Catalysis ◽  
Inert Gas ◽  
Natural Conditions ◽  
Metal Catalysis ◽  
Recent Advances ◽  
Gas Atmosphere

Transition-metal catalysis is out-grown from dry-boxes where the use of inert gas atmosphere and the exclusion of moisture have been essential. Such a restriction undoubtedly imposes limitations in the application of these reactions in organic synthesis and in the recycling of the catalysts. This article discusses some recent advances of rhodium-catalyzed carbon­carbon bond formations under the natural conditions of air and water.

Organocatalytic Atom-Transfer C(sp3)–H Oxidation

Synlett ◽  
2018 ◽  
Vol 29 (18) ◽  
pp. 2331-2336 ◽  
Author(s):  
Michael Hilinski ◽  
Shea Johnson ◽  
Logan Combee
Keyword(s):  
Transition Metal ◽  
Late Stage ◽  
Transition Metal Catalysis ◽  
Great Promise ◽  
Atom Transfer ◽  
Complex Molecules ◽  
Metal Catalysis ◽  
Iminium Salt ◽  
Site Selective

Predictably site-selective catalytic methods for intermolecular C(sp3)–H hydroxylation and amination hold great promise for the synthesis and late-stage modification of complex molecules. Transition-metal catalysis has been the most common approach for early investigations of this type of reaction. In comparison, there are far fewer ­reports of organocatalytic methods for direct oxygen or nitrogen insertion into C–H bonds. Herein, we provide an overview of early efforts in this area, with particular emphasis on our own recent development of an iminium salt that catalyzes both oxygen and nitrogen insertion.1 Introduction2 Background: C–H Oxidation Capabilities of Heterocyclic Oxidants3 Oxaziridine-Mediated Catalytic Hydroxylation4 Dioxirane-Mediated Catalytic Hydroxylation5 Iminium Salt Catalysis of Hydroxylation and Amination6 Conclusion and Outlook

Sign in / Sign up

Export Citation Format

Share Document