Recent Advances in Transition-Metal-Catalyzed (4+3)-Cycloadditions

Synthesis ◽  
2020 ◽  
Vol 52 (17) ◽  
pp. 2427-2449 ◽  
Author(s):  
Mark Lautens ◽  
Heather Lam
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Transition Metal Catalysts ◽  
Cope Rearrangement ◽  
Biologically Relevant ◽  
The Past ◽  
Gold Silver ◽  
Dual Activation ◽  
Metal Catalyzed ◽  
Palladium Platinum

A (4+3)-cycloaddition combines a four-atom synthon and three-atom synthon to form seven-membered rings. In the past decade, many improvements have been made to this class of cycloaddition, including excellent diastereo- and enantioselectivities, both intra- and intermolecularly. Through the strategic use of transition-metal catalysts, acids, bases, and organocatalysts, it is possible to perform the cycloaddition on a variety of substrates, generating novel seven-membered rings. With these advances, (4+3)-cycloaddition has also been applied to the synthesis of biologically relevant compounds and natural products. We exclude the cycloadditions of cyclic dienes such as furan, pyrrole, cyclohexadiene or cyclopentadiene as Chiu, Harmata, Mascareñas­ and others have recently published thorough reviews on that topic. We will however discuss the recent additions (2009–2020) to the literature for the (4+3)-cycloadditions involving other types of four-atom synthons.1 Introduction2 Rhodium2.1 Cyclopropanation/Cope Rearrangement2.2 C–H activation3 Gold, Silver4 Copper5 Palladium, Platinum, Iridium6 Dual-Activation7 Conclusion

Transition Metal Catalyzed C-H bond Activation/Functionalization and Annulation of Phthalazinones

2021 ◽  
Author(s):  
Chandrasekaran Sivaraj ◽  
Alagumalai Ramkumar ◽  
Nagesh Sankaran ◽  
THIRUMANAVELAN GANDHI
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Bond Activation ◽  
Bioactive Molecules ◽  
Structural Motifs ◽  
The Past ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

Phthalazinones and their higher congeners are commonly prevalent structural motifs that occur in natural products, bioactive molecules, and pharmaceuticals. In the past few decades transition metal-catalyzed reactions have received an...

Regioselective Transition-Metal-Catalyzed C–H Functionalization of Anilines

Synthesis ◽  
2018 ◽  
Vol 50 (14) ◽  
pp. 2693-2706 ◽  
Author(s):  
Jamie Leitch ◽  
Christopher Frost
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Building Blocks ◽  
Synthetic Methodology ◽  
Biologically Relevant ◽  
The Subject ◽  
Transition Metal Catalyzed ◽  
Biologically Relevant Molecules ◽  
Metal Catalyzed

Anilines are a vital synthetic core of pharmaceuticals, agrochemicals, natural products and building blocks. Metal-catalyzed C–H functionalization has emerged as a powerful tool to derivatize biologically relevant molecules. To this end, the derivation of anilines via catalytic C–H functionalization has been the subject of important new synthetic methodology. This review focuses on the tactics used to allow regioselective C–H functionalization of anilines.1 Introduction2 ortho-Selective C–H Functionalization2.1 Palladium2.2 Rhodium2.3 Ruthenium2.4 Nickel3 meta-Selective C–H Functionalization4 para-Selective C–H Functionalization5 Conclusion

Recent advance in NHC-palladium catalysis for alkynes chemistry: versatile synthesis and applications

2021 ◽  
Author(s):  
Jianxiao Li ◽  
Dan He ◽  
Zidong Lin ◽  
Wanqing Wu ◽  
Huanfeng Jiang
Keyword(s):  
Transition Metal ◽  
Palladium Catalysis ◽  
Metal Catalysts ◽  
Chemical Transformations ◽  
The Past ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

During the past decades, alkynes chemistry has attracted considerable attention owing to their unique and idiographic nucleophilic and electrophilic properties in transition-metal-catalyzed chemical transformations. Among the various metal catalysts, palladium...

scholarly journals Recent Advances in Transition-Metal-Free (4+3)-Annulations

Synthesis ◽  
2021 ◽  
Author(s):  
Heather Lam ◽  
Mark Lautens ◽  
Xavier Abel-Snape ◽  
Martin F. Köllen
Keyword(s):  
Transition Metal ◽  
Boronic Acid ◽  
Lewis Acids ◽  
Acid Catalysis ◽  
Heterocyclic Carbenes ◽  
Bronsted Acids ◽  
Metal Free ◽  
Previous Review ◽  
Dual Activation ◽  
Metal Catalyzed

Abstract(4+3)-Annulations are incredibly versatile reactions which combine a 4-atom synthon and a 3-atom synthon to form both 7-membered carbocycles as well as heterocycles. We have previously reviewed transition-metal-catalyzed (4+3)-annulations. In this review, we will cover examples involving bases, NHCs, phosphines, Lewis and Brønsted acids as well as some rare examples of boronic acid catalysis and photocatalysis. In analogy to our previous review, we exclude annulations involving cyclic dienes like furan, pyrrole, cyclohexadiene or cyclopentadiene, as Chiu, Harmata, Fernándes and others have recently published reviews encompassing such substrates. We will however discuss the recent additions (2010–2020) to the literature on (4+3)-annulations involving other types of 4-atom-synthons.1 Introduction2 Bases3 Annulations Using N-Heterocyclic Carbenes3.1 N-Heterocyclic Carbenes (NHCs)3.2 N-Heterocyclic Carbenes and Base Dual-Activation4 Phosphines5 Acids5.1 Lewis Acids5.2 Brønsted Acids6 Boronic Acid Catalysis and Photocatalysis7 Conclusion

Transition-Metal-Catalyzed Reactions Involving Arynes

Synthesis ◽  
2017 ◽  
Vol 50 (01) ◽  
pp. 1-16 ◽  
Author(s):  
Santosh Mhaske ◽  
Ranjeet Dhokale
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Total Synthesis ◽  
Scientific Community ◽  
Multicomponent Reactions ◽  
Polycyclic Aromatic Compounds ◽  
Polycyclic Aromatic ◽  
Transition Metal Catalyzed ◽  
Catalyzed Reactions ◽  
Metal Catalyzed

The plethora of transformations attainable by the transition-metal-catalyzed reactions of arynes has found immense contemporary interest in the scientific community. This review highlights the scope and importance of transition-metal-catalyzed aryne reactions in the field of synthetic organic chemistry reported to date. It covers transformations achieved by the combination of arynes and various transition metals, which provide a facile access to a biaryl motif, fused polycyclic aromatic compounds, different novel carbocycles, various heterocycles, and complex natural products.1 Introduction2 Insertion of Arynes3 Annulation of Arynes4 Cycloaddition of Arynes5 Multicomponent Reactions of Arynes6 Miscellaneous Reactions of Arynes7 Total Synthesis of Natural Products Using Arynes8 Conclusion

Soluble polymer-supported organocatalysts

2012 ◽  
Vol 85 (3) ◽  
pp. 493-509 ◽  
Author(s):  
Yun-Chin Yang ◽  
David E. Bergbreiter
Keyword(s):  
Transition Metal ◽  
Organic Synthesis ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Soluble Polymer ◽  
Soluble Polymers ◽  
The Past ◽  
Polymer Supports ◽  
Polymer Supported ◽  
Simple Product

Organocatalysts have been extensively studied for the past few decades as alternatives to transition-metal catalysts. Immobilizing organocatalysts on polymer supports allows easy recovery and simple product purification after a reaction. Select examples of recent reports that describe the potential advantages of using soluble polymers to prepare soluble polymer-supported organocatalysts useful in organic synthesis are reviewed.

The C–H functionalization of N-alkoxycarbamoyl indoles by transition metal catalysis

2021 ◽  
Vol 19 (37) ◽  
pp. 7949-7969
Author(s):  
Prasanjit Ghosh ◽  
Sajal Das
Keyword(s):  
Natural Products ◽  
Transition Metal ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Indole and its congeners are ubiquitous nitrogen containing organic scaffolds found in a plethora of natural products. This review aims to highlight the transition-metal catalyzed C–H functionalization of N-alkoxycarbamoyl indoles.

Directing-Group-Assisted Transition-Metal-Catalyzed Direct C–H Oxidative Annulation of Arenes with Alkynes for Facile Construction of Various Oxygen Heterocycles

Synthesis ◽  
2020 ◽  
Vol 52 (07) ◽  
pp. 993-1006 ◽  
Author(s):  
Guanghua Kuang ◽  
Guangyuan Liu ◽  
Xingxing Zhang ◽  
Naihao Lu ◽  
Yiyuan Peng ◽  
...  
Keyword(s):  
Transition Metal ◽  
Noble Metals ◽  
Metal Catalysts ◽  
Transition Metal Catalysts ◽  
Research Papers ◽  
Recent Advances ◽  
Oxygen Heterocycles ◽  
Directing Group ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

The most recent advances in the construction of oxygen heterocycles by the directing-group-assisted transition-metal-catalyzed direct oxidative annulation of arenes with diverse alkynes are summarized in this review. More than 140 recent research papers and many closely related reviews are referenced in this paper. Nine different oxygen heterocycles frameworks are discussed. Several traditional transition-metal catalysts as well as some classical non-noble metals are utilized to promote the annulation. Three plausible controlling models are disclosed to clarify the excellent regioselectivity outcomes achieved in case of unsymmetrical alkyne substrates.1 Introduction2 Coumarins3 I socoumarins and Their Analogues4 2-Pyrones and Their Analogues5 Chromones and Chroman-4-ones6 Chromenes and Isochromenes7 Fused Polycyclic Oxygen Heteroaromatics8 Benzofurans, Dihydrobenzofurans, and Furans9 Phthalides and Benzofuranones10 Benzoxepines11 Conclusion

scholarly journals Advances in the Preparation of Fluorinated Isoquinolines: A Decade of Progress

2017 ◽  
Vol 2017 ◽  
pp. 1-15 ◽  
Author(s):  
Joseph C. Sloop
Keyword(s):  
Transition Metal ◽  
Functional Groups ◽  
Synthetic Methods ◽  
Ring Systems ◽  
Heterocyclic Molecules ◽  
The Past ◽  
Ring Assembly ◽  
Metal Catalyzed ◽  
Synthetic Approaches ◽  
Isoquinoline Derivatives

Heterocyclic molecules incorporating fluorinated isoquinoline components are found in many medicinally and agriculturally important bioactive products as well as industrially impactful materials. Within the past decade, a variety of isoquinolinic ring assembly techniques has enabled the introduction of diverse fluorine-containing functionalities which can enhance potential bioactivity and industrial utility. This review examines recent noncatalyzed and transition metal catalyzed synthetic approaches to the assembly of isoquinoline derivatives that are ring-fluorinated and/or result in the incorporation of fluorine-containing functional groups. Specifically, efficient synthetic methods and regioselectivity in the incorporation of functional groups into isoquinoline ring systems are examined.

scholarly journals Synthesis of Medium-Sized Heterocycles by Transition-Metal-Catalyzed Intramolecular Cyclization

Molecules ◽  
2020 ◽  
Vol 25 (14) ◽  
pp. 3147 ◽  
Author(s):  
Mickael Choury ◽  
Alexandra Basilio Lopes ◽  
Gaëlle Blond ◽  
Mihaela Gulea
Keyword(s):  
Transition Metal ◽  
Intramolecular Cyclization ◽  
Biologically Active ◽  
Conformational Constraints ◽  
Synthesis Strategy ◽  
Gold Silver ◽  
Copper Gold ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed ◽  
Active Natural

Medium-sized heterocycles (with 8 to 11 atoms) constitute important structural components of several biologically active natural compounds and represent promising scaffolds in medicinal chemistry. However, they are under-represented in the screening of chemical libraries as a consequence of being difficult to access. In particular, methods involving intramolecular bond formation are challenging due to unfavorable enthalpic and entropic factors, such as transannular interactions and conformational constraints. The present review focuses on the synthesis of medium-sized heterocycles by transition-metal-catalyzed intramolecular cyclization, which despite its drawbacks remains a straightforward and attractive synthesis strategy. The obtained heterocycles differ in their nature, number of heteroatoms, and ring size. The methods are classified according to the metal used (palladium, copper, gold, silver), then subdivided according to the type of bond formed, namely carbon–carbon or carbon–heteroatom.

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