Recent Progress in Radical Decarboxylative Functionalizations Enabled by Transition-Metal (Ni, Cu, Fe, Co or Cr) Catalysis

Synthesis ◽  
2020 ◽  
Vol 53 (01) ◽  
pp. 1-29
Author(s):  
Yahu A Liu ◽  
Xuebin Liao ◽  
Hui Chen
Keyword(s):  
Transition Metal ◽  
Carboxylic Acids ◽  
Recent Progress ◽  
Bond Formation ◽  
Transition Metal Catalysis ◽  
Great Success ◽  
Chemical Transformations ◽  
Metal Catalysis ◽  
Redox Active ◽  
Aliphatic Carboxylic Acids

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

scholarly journals Enamine/Transition Metal Combined Catalysis: Catalytic Transformations Involving Organometallic Electrophilic Intermediates

2019 ◽  
Vol 377 (6) ◽  
Author(s):  
Samson Afewerki ◽  
Armando Córdova
Keyword(s):  
Transition Metal ◽  
Metal Complex ◽  
Carbonyl Compounds ◽  
Transition Metal Catalysis ◽  
Chemical Transformations ◽  
Considerable Effort ◽  
Metal Catalysis ◽  
First Report ◽  
Wide Range ◽  
Selective Chemical

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.

Diacyl peroxides, practical reagents as aryl and alkyl radical sources

2021 ◽  
Author(s):  
Han Liu ◽  
Jin-Tao Yu ◽  
Changduo Pan
Keyword(s):  
Transition Metal ◽  
Carboxylic Acids ◽  
Alkyl Radical ◽  
Transition Metal Catalysis ◽  
Thermal Transition ◽  
Metal Catalysis ◽  
Radical Initiators

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...

Recent Progress on Radical Decarboxylative Alkylation for Csp3–C Bond Formation

Synthesis ◽  
2017 ◽  
Vol 49 (24) ◽  
pp. 5263-5284 ◽  
Author(s):  
Hongli Bao ◽  
Yajun Li ◽  
Liang Ge ◽  
Munira Muhammad
Keyword(s):  
Carboxylic Acids ◽  
Recent Progress ◽  
Bond Formation ◽  
Stepping Stone ◽  
Recent Advances ◽  
Aliphatic Carboxylic Acids ◽  
Further Development

Radical decarboxylation has emerged as an attractive method for the formation of C–C bonds starting from easily accessible carboxylic acids. In this review, we attempt to bring the readers up to date in this rapidly expanding field. Specifically, we will cover recent advances in Csp3–C bond formation via the radical decarboxylation of aliphatic carboxylic acids and their activated forms, such as N-hydroxyphthalimide esters (NHP esters), alkyl diacyl peroxides, alkyl peresters, and aryliodine(III) dicarboxylates. The scope and limitation of these transformations will be discussed, highlighting gaps in knowledge and research and examining the mechanisms underlying radical decarboxylation. We aim to make this review a stepping stone for further development in this field.1 Introduction2 Aliphatic Carboxylic Acids3 N-Hydroxyphthalimide Esters (NHP Esters)4 Alkyl Diacyl Peroxides5 Alkyl Peresters6 Aryliodine(III) Dicarboxylates7 Conclusion

Metal-Free Catalytic Aromatic C–H Borylation

Synlett ◽  
2020 ◽  
Vol 31 (19) ◽  
pp. 1857-1861
Author(s):  
Hua Zhang ◽  
Li Wang
Keyword(s):  
Transition Metal ◽  
Recent Progress ◽  
Rapid Development ◽  
Transition Metal Catalysis ◽  
Mechanistic Studies ◽  
Metal Catalysis ◽  
Promising Alternative ◽  
Metal Free ◽  
History Of ◽  
Near Future

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.

Catalytic asymmetric synthesis of polysubstituted spirocyclopropyl oxindoles: organocatalysis versus transition metal catalysis

2015 ◽  
Vol 2 (7) ◽  
pp. 849-858 ◽  
Author(s):  
Zhong-Yan Cao ◽  
Jian Zhou
Keyword(s):  
Transition Metal ◽  
Asymmetric Synthesis ◽  
Recent Progress ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Catalytic Asymmetric Synthesis ◽  
Versus Transition ◽  
Catalytic Asymmetric

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

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.

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