scholarly journals Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Molecules ◽  
2020 ◽  
Vol 25 (24) ◽  
pp. 5900
Author(s):  
Hamid Azizollahi ◽  
José-Antonio García-López

The functionalization of C–H bonds has become a major thread of research in organic synthesis that can be assessed from different angles, for instance depending on the type of catalyst employed or the overall transformation that is carried out. This review compiles recent progress in synthetic methodology that merges the functionalization of C–H bonds along with the cleavage of C–C bonds, either in intra- or intermolecular fashion. The manuscript is organized in two main sections according to the type of substrate in which the cleavage of the C–C bond takes place, basically attending to the scission of strained or unstrained C–C bonds. Furthermore, the related research works have been grouped on the basis of the mechanistic aspects of the different transformations that are carried out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates are involved; (b) processes occurring via radical intermediates generated through the use of radical initiators or photochemically; and (c) reactions that are catalyzed or mediated by suitable Lewis or Brønsted acid or bases, where molecular rearrangements take place. Thus, throughout the review a wide range of synthetic approaches show that the combination of C–H and C–C cleavage in single synthetic operations can serve as a platform to achieve complex molecular skeletons in a straightforward manner, among them interesting carbo- and heterocyclic scaffolds.

Author(s):  
Ke-Yin Ye ◽  
Jun-Song Zhong ◽  
Yi Yu ◽  
Zhaojiang Shi

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...


2019 ◽  
Vol 377 (6) ◽  
Author(s):  
Samson Afewerki ◽  
Armando Córdova

AbstractThe concept of merging enamine activation catalysis with transition metal catalysis is an important strategy, which allows for selective chemical transformations not accessible without this combination. The amine catalyst activates the carbonyl compounds through the formation of a reactive nucleophilic enamine intermediate and, in parallel, the transition metal activates a wide range of functionalities such as allylic substrates through the formation of reactive electrophilic π-allyl-metal complex. Since the first report of this strategy in 2006, considerable effort has been devoted to the successful advancement of this technology. In this chapter, these findings are highlighted and discussed.


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

2021 ◽  
Author(s):  
Han Liu ◽  
Jin-Tao Yu ◽  
Changduo Pan

Diacyl peroxides, which can be easily synthesized from corresponding carboxylic acids, are commonly utilized as radical initiators and one electron oxidants. Under thermal, transition-metal catalysis or irradiation conditions the cleavage...


Synthesis ◽  
2018 ◽  
Vol 51 (03) ◽  
pp. 612-628 ◽  
Author(s):  
Janakiram Vaitla ◽  
Annette Bayer

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


Synlett ◽  
2020 ◽  
Vol 31 (19) ◽  
pp. 1857-1861
Author(s):  
Hua Zhang ◽  
Li Wang

In recent decades, C–H borylation has undergone rapid development and has become one of the most important and efficient methods for the synthesis of organoboron compounds. Although transition-metal catalysis dominates C–H borylation, the metal-free approach has emerged as a promising alternative strategy. This article briefly summarizes the history of metal-free aromatic C–H borylation, including early reports on electrophilic C–H borylation and recent progress in metal-free catalytic intermolecular C–H borylation; it also highlights our recent work on BF3·Et2O-catalyzed C2–H borylation of hetarenes. Despite these recent advances, comprehensive mechanistic studies on various metal-free catalytic aromatic C–H borylations and novel processes with a wider substrate scope are eagerly expected in the near future.


2015 ◽  
Vol 2 (7) ◽  
pp. 849-858 ◽  
Author(s):  
Zhong-Yan Cao ◽  
Jian Zhou

Recent progress in catalytic asymmetric synthesis of spirocyclopropyl oxindoles via organocatalysis and transition metal catalysis are summarized and discussed.


Author(s):  
Maximilian Selt ◽  
Barbara Gleede ◽  
Robert Franke ◽  
Andreas Stenglein ◽  
Siegfried R. Waldvogel

Abstract3,3′,5,5’-Tetramethyl-2,2′-biphenol is well known as an outstanding building block for ligands in transition-metal catalysis and is therefore of particular industrial interest. The electro-organic method is a powerful, sustainable, and efficient alternative to conventional synthetic approaches to obtain symmetric and non-symmetric biphenols. Here, we report the successive scale-up of the dehydrogenative anodic homocoupling of 2,4-dimethylphenol (4) from laboratory scale to the technically relevant scale in highly modular narrow gap flow electrolysis cells. The electrosynthesis was optimized in a manner that allows it to be easily adopted to different scales such as laboratory, semitechnical and technical scale. This includes not only the synthesis itself and its optimization but also a work-up strategy of the desired biphenols for larger scale. Furthermore, the challenges such as side reactions, heat development and gas evolution that arose during optimization are also discussed in detail. We have succeeded in obtaining yields of up to 62% of the desired biphenol.


Synthesis ◽  
2020 ◽  
Vol 53 (01) ◽  
pp. 1-29
Author(s):  
Yahu A Liu ◽  
Xuebin Liao ◽  
Hui Chen

AbstractAliphatic carboxylic acids are abundant in natural and synthetic sources and are widely used as connection points in many chemical transformations. Radical decarboxylative functionalization promoted by transition-metal catalysis has achieved great success, enabling carboxylic acids to be easily transformed into a wide variety of products. Herein, we highlight the recent advances made on transition-metal (Ni, Cu, Fe, Co or Cr) catalyzed C–X (X = C, N, H, O, B, or Si) bond formation as well as syntheses of ketones, amino acids, alcohols, ethers and difluoromethyl derivatives via radical decarboxylation of carboxylic acids or their derivatives, including, among others, redox-active esters (RAEs), anhydrides, and diacyl peroxides.1 Introduction2 Ni-Catalyzed Decarboxylative Functionalizations3 Cu-Catalyzed Decarboxylative Functionalizations4 Fe-Catalyzed Decarboxylative Functionalizations5 Co- and Cr-Catalyzed Decarboxylative Functionalizations6 Conclusions


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