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

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 Amine-Catalyzed Decarboxylative Aldol Reaction of β-Ketocarboxylic Acids with Trifluoropyruvates

Molecules ◽  
2019 ◽  
Vol 24 (15) ◽  
pp. 2773
Author(s):  
Ryouta Kawanishi ◽  
Shinya Hattori ◽  
Seiji Iwasa ◽  
Kazutaka Shibatomi
Keyword(s):  
Carboxylic Acids ◽  
Tertiary Amine ◽  
Bond Formation ◽  
Aldol Reaction ◽  
Quaternary Carbon ◽  
Chiral Amine ◽  
Enantioselective Reaction ◽  
High Yields ◽  
Aliphatic Carboxylic Acids

Decarboxylative aldol reaction of aliphatic carboxylic acids is a useful method for C–C bond formation because carboxylic acids are an easily available class of compounds. In this study, we found that the decarboxylative aldol reaction of tertiary β-ketocarboxylic acids and trifluoropyruvates proceeded smoothly to yield the corresponding aldol products in high yields and with high diastereoselectivity in the presence of a tertiary amine catalyst. In this reaction, we efficiently constructed a quaternary carbon center and an adjacent trifluoromethylated carbon center. This protocol was also extended to an enantioselective reaction with a chiral amine catalyst, and the desired product was obtained with up to 73% enantioselectivity.

scholarly journals Recent advances in copper-catalyzed C–H bond amidation

2015 ◽  
Vol 11 ◽  
pp. 2209-2222 ◽  
Author(s):  
Jie-Ping Wan ◽  
Yanfeng Jing
Keyword(s):  
Functional Groups ◽  
Organic Synthesis ◽  
Recent Progress ◽  
Bond Formation ◽  
Carbon Sources ◽  
Copper Catalysis ◽  
Recent Advances

Copper catalysis has been known as a powerful tool for its ubiquitous application in organic synthesis. One of the fundamental utilities of copper catalysis is in the C–N bond formation by using carbon sources and nitrogen functional groups such as amides. In this review, the recent progress in the amidation reactions employing copper-catalyzed C–H amidation is summarized.

Recent advances in the synthesis of ent-kaurane diterpenoids

2021 ◽  
Author(s):  
Xiangbo Zhao ◽  
Bastien Cacherat ◽  
Qifei Hu ◽  
Dawei Ma
Keyword(s):  
Recent Progress ◽  
Bond Formation ◽  
Total Syntheses ◽  
Recent Advances

In this review, recent progress in total syntheses of ent-kaurane diterpenoids from 2015 to date are presented, and key transformations for strategic bond formation are highlighted.

Generation of Phosphoranyl Radicals via Photoredox Catalysis Enables Voltage–Independent Activation of Strong C–O Bonds

2018 ◽  
Author(s):  
Erin Stache ◽  
Alyssa B. Ertel ◽  
Tomislav Rovis ◽  
Abigail G. Doyle
Keyword(s):  
Carboxylic Acids ◽  
Functional Groups ◽  
Single Step ◽  
Direct Access ◽  
Photoredox Catalysis ◽  
Acyl Radical ◽  
Synthetic Strategy ◽  
Acyl Radicals ◽  
Benzyl Radicals ◽  
Aliphatic Carboxylic Acids

Alcohols and carboxylic acids are ubiquitous functional groups found in organic molecules that could serve as radical precursors, but C–O bonds remain difficult to activate. We report a synthetic strategy for direct access to both alkyl and acyl radicals from these ubiquitous functional groups via photoredox catalysis. This method exploits the unique reactivity of phosphoranyl radicals, generated from a polar/SET crossover between a phosphine radical cation and an oxygen centered nucleophile. We first show the desired reactivity in the reduction of benzylic alcohols to the corresponding benzyl radicals with terminal H-atom trapping to afford the deoxygenated product. Using the same method, we demonstrate access to synthetically versatile acyl radicals which enables the reduction of aromatic and aliphatic carboxylic acids to the corresponding aldehydes with exceptional chemoselectivity. This protocol also transforms carboxylic acids to heterocycles and cyclic ketones via intramolecular acyl radical cyclizations to forge new C–O, C–N and C–C bonds in a single step.

Recent Advances on C-Se Bond-forming Reactions at Low and Room Temperature

2020 ◽  
Vol 23 (28) ◽  
pp. 3206-3225 ◽  
Author(s):  
Amol D. Sonawane ◽  
Mamoru Koketsu
Keyword(s):  
Room Temperature ◽  
Bond Formation ◽  
Bond Forming ◽  
Material Chemistry ◽  
Recent Advances ◽  
Bond Forming Reactions ◽  
Bond Formation Reactions

: Over the last decades, many methods have been reported for the synthesis of selenium- heterocyclic scaffolds because of their interesting reactivities and applications in the medicinal as well as in the material chemistry. This review describes the recent numerous useful methodologies on C-Se bond formation reactions which were basically carried out at low and room temperature.

scholarly journals Deep learning: a new tool for photonic nanostructure design

2020 ◽  
Vol 2 (3) ◽  
pp. 1007-1023 ◽  
Author(s):  
Ravi S. Hegde
Keyword(s):  
Deep Learning ◽  
Recent Progress ◽  
Further Development

We review recent progress in the application of Deep Learning (DL) techniques for photonic nanostructure design and provide a perspective on current limitations and fruitful directions for further development.

Improved QSAR Analysis of the Toxicity of Aliphatic Carboxylic Acids

2003 ◽  
Vol 73 (11) ◽  
pp. 1792-1798 ◽  
Author(s):  
F. P. Maguna ◽  
M. B. Ninez ◽  
N. B. Okulik ◽  
E. A. Castro
Keyword(s):  
Carboxylic Acids ◽  
Qsar Analysis ◽  
Aliphatic Carboxylic Acids
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