Transition-metal-catalyzed nucleophilic dearomatization of electron-deficient heteroarenes

Powerful Method ◽

Metal Catalysis ◽

Unique Method ◽

Transition-metal-catalyzed nucleophilic dearomatization of electron-deficient heteroarenes, such as pyridines, quinolines, isoquinolines and nitroindoles, has become a powerful method for the access of unsaturated heterocycles in recent decades. This short review summarizes nucleophilic dearomatization of electron-deficient heteroarenes with carbon- and heteroatom-based nucleophiles via transition-metal catalysis. A great number of functionalized heterocycles were obtained in this transformation. Importantly, many of these reactions were carried out in an enantioselective manner by means of asymmetric catalysis, providing a unique method for the construction of enantioenriched heterocycles. 1 Introduction 2 Transition-metal-catalyzed nucleophilic dearomatization of heteroarenes via alkynylation 3 Transition-metal-catalyzed nucleophilic dearomatization of heteroarenes via arylation 4 Transition-metal-catalyzed nucleophilic dearomatization of heteroarenes with other nucleophiles 5 Transition-metal-catalyzed nucleophilic dearomatization with nucleophiles formed in situ 6 Conclusion and outlook

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

Organic & Biomolecular Chemistry ◽

10.1039/d1ob01121a ◽

2021 ◽

Vol 19 (37) ◽

pp. 7949-7969

Author(s):

Prasanjit Ghosh ◽

Sajal Das

Keyword(s):

Natural Products ◽

Transition Metal ◽

Metal Catalysis ◽

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.

Recent development of synthetic preparation methods for guanidines via transition metal catalysis

Chemical Communications ◽

10.1039/c4cc05291a ◽

2015 ◽

Vol 51 (2) ◽

pp. 254-265 ◽

Cited By ~ 81

Author(s):

Wen-Xiong Zhang ◽

Ling Xu ◽

Zhenfeng Xi

Keyword(s):

Transition Metal ◽

Preparation Methods ◽

Metal Catalysis ◽

Catalyzed Reactions ◽

This article provides an overview of guanidine synthesis via transition-metal-catalyzed reactions including cycloaddition, guanylation and tandem guanylation/cyclization.

Recent Developments in Transition-Metal Catalyzed Direct C–H Alkenylation, Alkylation, and Alkynylation of Azoles

Molecules ◽

10.3390/molecules25214970 ◽

2020 ◽

Vol 25 (21) ◽

pp. 4970

Author(s):

Su Chen ◽

Prabhat Ranjan ◽

Leonid G. Voskressensky ◽

Erik V. Van der Eycken ◽

Upendra K. Sharma

Keyword(s):

Transition Metal ◽

Significant Progress ◽

Metal Catalysis ◽

Bond Functionalization ◽

Recent Advances ◽

Regioselective Alkylation ◽

Recent Developments ◽

The transition metal-catalyzed C–H bond functionalization of azoles has emerged as one of the most important strategies to decorate these biologically important scaffolds. Despite significant progress in the C–H functionalization of various heteroarenes, the regioselective alkylation and alkenylation of azoles are still arduous transformations in many cases. This review covers recent advances in the direct C–H alkenylation, alkylation and alkynylation of azoles utilizing transition metal-catalysis. Moreover, the limitations of different strategies, chemoselectivity and regioselectivity issues will be discussed in this review.

Transition metal-catalyzed direct nucleophilic addition of C–H bonds to carbon–heteroatom double bonds

Chemical Science ◽

10.1039/c3sc53115e ◽

2014 ◽

Vol 5 (6) ◽

pp. 2146-2159 ◽

Cited By ~ 255

Author(s):

Xi-Sha Zhang ◽

Kang Chen ◽

Zhang-Jie Shi

Keyword(s):

Transition Metal ◽

Nucleophilic Addition ◽

Grignard Reaction ◽

Double Bonds ◽

Metal Catalysis ◽

Compared with the traditional Grignard reaction, direct insertion of polar double bonds to C–H bonds via transition-metal catalysis is ideal from the viewpoint of atom-, step- and cost-economy and the avoidance of the waste emission, as well as of the complex manipulation of sensitive reagents.

Transition Metal-Catalyzed Enantioselective α-Arylation of Carbonyl Compounds to Give Tertiary Stereocenters

Synthesis ◽

10.1055/a-1560-5245 ◽

2021 ◽

Author(s):

Manuel Orlandi ◽

Margarita Escudero-Casao ◽

Giulia Licini

Keyword(s):

Natural Products ◽

Transition Metal ◽

Carbonyl Group ◽

Carbonyl Compounds ◽

Short Review ◽

Biologically Active ◽

Metal Catalysis ◽

Quaternary Stereocenters ◽

Enantioenriched α-aryl carbonyl compounds are ubiquitous in natural products and biologically active compounds. Their synthesis has been explored over the last few decades and several methods now exist that allow for the enantioselective formation of a C(sp3)-C(sp2) bond in α-position to a carbonyl group. However, although the formation of quaternary stereocenters has been fairly well established, the enantioselective formation of tertiary stereocenters proved more challenging due to facile product post-reaction racemization. In this short review, we summarize the methods reported so far for the asymmetric α-arylation of enolates and analogues that rely on transition metal catalysis.

Synthesis of N-Heterocycles via Transition-Metal-Catalyzed Tandem Addition/Cyclization of a Nitrile

Synthesis ◽

10.1055/s-0039-1691561 ◽

2020 ◽

Vol 52 (06) ◽

pp. 819-833 ◽

Cited By ~ 5

Author(s):

Jen-Chieh Hsieh ◽

Haw-Lih Su

Keyword(s):

Transition Metal ◽

Lewis Acid ◽

Nucleophilic Addition ◽

Radical Addition ◽

Late Transition Metal ◽

Metal Catalysis ◽

Late Transition ◽

The diverse methodologies to synthesize N-heterocycles through transition-metal-catalyzed cascade addition/cyclization of a nitrile are discussed in this review. Aspects relating to three types of transition-metal-catalyzed addition of a nitrile with subsequent cyclization include (1) a transition-metal acting as a Lewis acid to accelerate the nucleophilic addition of a nitrile, (2) the late-transition-metal-catalyzed 1,2-insertion of a nitrile, and (3) an in situ generated radical by transition-metal catalysis to implement a radical addition/cyclization tandem reaction. Applications for the synthesis of natural alkaloids, their derivatives, and some bioactive compounds are also summarized herein.1 Introduction2 Nucleophilic Addition of a Nitrile Accelerated by a Lewis Acid2.1 Late-Transition-Metal Catalysis2.2 Early-Transition-Metal Catalysis2.3 Lanthanide-Metal Catalysis2.4 Cyclization from N-Arylnitriliums3 Transition-Metal-Catalyzed Insertion of a Nitrile4 Transition-Metal-Catalyzed Radical Addition of a Nitrile5 Conclusions

Peptide macrocyclization by transition metal catalysis

Chemical Society Reviews ◽

10.1039/c9cs00366e ◽

2020 ◽

Vol 49 (7) ◽

pp. 2039-2059 ◽

Cited By ~ 7

Author(s):

Daniel G. Rivera ◽

Gerardo M. Ojeda-Carralero ◽

Leslie Reguera ◽

Erik V. Van der Eycken

Keyword(s):

Transition Metal ◽

Metal Catalysis ◽

Conformational Constraints ◽

Catalyzed Reactions ◽

Peptide macrocyclization continues expanding with the development of novel transition metal-catalyzed reactions capable of both introducing conformational constraints and generating diversity at the ring-closing moiety.

Recent Advances in Decarboxylative Conversions of Cyclic Carbonates and Beyond

Synthesis ◽

10.1055/a-1715-7413 ◽

2021 ◽

Author(s):

Biwei Yan ◽

Wusheng Guo

Keyword(s):

Transition Metal ◽

Catalytic System ◽

Research Work ◽

Building Blocks ◽

Short Review ◽

Cyclic Carbonates ◽

Metal Catalysis ◽

Recent Advances ◽

Functionalized cyclic organic carbonates have emerged as valuable building blocks for the construction of interesting and useful molecules upon decarboxylation under transition metal catalysis in recent years. With suitable catalytic system, the development of chemo-, regio-, stereo- and enantioselective methods for the synthesis of useful and interesting compounds has advanced greatly. On the basis of previous research work on this topic, this short review will highlight the synthetic potential of cyclic carbonates under transition metal catalysis in last two years. 1 Introduction 2 Transition metal catalyzed decarboxylation of vinyl cyclic carbonates 3 Zwitterionic enolate chemistry based on transition metal catalysis 4 Decarboxylation of alkynyl cyclic carbonates and dioxazolones 5 Conclusions and perspectives

C–H functionalization of quinazolinones by transition metal catalysis

Organic & Biomolecular Chemistry ◽

10.1039/d0ob00742k ◽

2020 ◽

Vol 18 (24) ◽

pp. 4497-4518 ◽

Cited By ~ 6

Author(s):

Prasanjit Ghosh ◽

Bhaskar Ganguly ◽

Sajal Das

Keyword(s):

Natural Products ◽

Transition Metal ◽

Important Class ◽

Metal Catalysis ◽

Bond Functionalization ◽

Quinazolinone and its derivatives are an important class of heterocyclic scaffolds in pharmaceuticals and natural products. This review provides the recent research advances in the transition metal catalyzed selective C–H bond functionalization of quinazolinone.

Merging photoredox catalysis with transition metal catalysis: site-selective C4 or C5-H phosphonation of 8-aminoquinoline amides

Organic Chemistry Frontiers ◽

10.1039/c7qo00305f ◽

2017 ◽

Vol 4 (10) ◽

pp. 1981-1986 ◽

Cited By ~ 33

Author(s):

Huijie Qiao ◽

Suyan Sun ◽

Yue Zhang ◽

Hongmei Zhu ◽

Xiaomeng Yu ◽

...

Keyword(s):

Transition Metal ◽

Photoredox Catalysis ◽

Metal Catalysis ◽

Metal Catalyzed ◽

Site Selective

A simple and efficient protocol for the transition metal-catalyzed site-selective C–H phosphonation of 8-aminoquinoline at the C4 or C5 positions via a photoredox process was developed.