Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C–N Bond Formation from Nonactivated Aliphatic Carboxylic Acids

AbstractOrganobromine compounds are extremely useful in organic synthesis. In this perspective, a focused discussion on some recent advancements in C–Br bond-forming reactions is presented.1 Introduction2 Selected Recent Advances2.1 Catalytic Asymmetric Bromopolycyclization of Olefinic Substrates2.2 Catalytic Asymmetric Intermolecular Bromination2.3 Some New Catalysts and Reagents for Bromination2.4 Catalytic Site-Selective Bromination of Aromatic Compounds2.5 sp3 C–H Bromination via Atom Transfer/Cross-Coupling3 Outlook

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Silver-Mediated C−S Cross-Coupling of Di(pyrimidin-2-yl) Disulfides with Aliphatic Carboxylic Acids

ChemistrySelect ◽

10.1002/slct.201601870 ◽

2017 ◽

Vol 2 (3) ◽

pp. 1140-1143 ◽

Cited By ~ 3

Author(s):

Wen-Juan Wang ◽

Xiao-Jun Liu ◽

Xi-Cun Wang

Keyword(s):

Carboxylic Acids ◽

Cross Coupling ◽

Aliphatic Carboxylic Acids

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

Synthesis ◽

10.1055/s-0036-1590935 ◽

2017 ◽

Vol 49 (24) ◽

pp. 5263-5284 ◽

Cited By ~ 29

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

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Direct C(sp3)–H Activation of Carboxylic Acids

Synthesis ◽

10.1055/s-0039-1690720 ◽

2019 ◽

Vol 52 (04) ◽

pp. 479-488 ◽

Cited By ~ 2

Author(s):

Alexander Uttry ◽

Manuel van Gemmeren

Keyword(s):

Carboxylic Acid ◽

General Solution ◽

Carboxylic Acids ◽

Bond Activation ◽

Acid Moiety ◽

Group Approach ◽

Research Fields ◽

Directing Group ◽

Aliphatic Carboxylic Acids

Carboxylic acids are important in a variety of research fields and applications. As a result, substantial efforts have been directed towards the C–H functionalization of such compounds. While the use of the carboxylic acid moiety as a native directing group for C(sp2)–H functionalization reactions is well established, as yet there is no general solution for the C(sp3)–H activation of aliphatic carboxylic acids and most endeavors have instead relied on the introduction of stronger directing groups. Recently however, novel ligands, tools, and strategies have emerged, which enable the use of free aliphatic carboxylic acids in C–H-activation-based transformations.1 Introduction2 Challenges in the C(sp3)–H Bond Activation of Carboxylic Acids3 The Lactonization of Aliphatic Carboxylic Acids4 The Directing Group Approach5 The Direct C–H Arylation of Aliphatic Carboxylic Acids6 The Direct C–H Olefination of Aliphatic Carboxylic Acids7 The Direct C–H Acetoxylation of Aliphatic Carboxylic Acids8 Summary

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Silver-Mediated Decarboxylative C–S Cross-Coupling of Aliphatic Carboxylic Acids under Mild Conditions

Organic Letters ◽

10.1021/ol502144c ◽

2014 ◽

Vol 16 (17) ◽

pp. 4586-4589 ◽

Cited By ~ 83

Author(s):

Peng-Fei Wang ◽

Xiao-Qing Wang ◽

Jian-Jun Dai ◽

Yi-Si Feng ◽

Hua-Jian Xu

Keyword(s):

Carboxylic Acids ◽

Cross Coupling ◽

Mild Conditions ◽

Aliphatic Carboxylic Acids

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

Synthesis ◽

10.1055/s-0040-1707273 ◽

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

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7,10-Dibromo-2,3-dicyanopyrazinophenanthrene Aggregates as a Photosensitizer for Nickel-Catalyzed Aryl Esterification

Synlett ◽

10.1055/s-0040-1720887 ◽

2021 ◽

Author(s):

Xiaoqiang Yu ◽

Min He ◽

Shilei Yang ◽

Ming Bao

Keyword(s):

Visible Light ◽

Carboxylic Acids ◽

Bond Formation ◽

Cross Coupling ◽

Aryl Halides ◽

Ni Catalyst ◽

Coupling Reactions ◽

Formation Reaction ◽

Cross Coupling Reactions ◽

Reaction Proceeds

AbstractSelf-assembled aggregates of 7,10-dibromo-2,3-dicyanopyrazinophenanthrene which act as a new organophotocatalyst in combination with Ni catalyst for the Caryl–Oacyl cross-coupling reactions of carboxylic acids with aryl halides are described. This visible-light-induced Caryl–Oacyl bond-formation reaction proceeds smoothly to afford aryl esters with satisfactory to excellent yields.

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

Molecules ◽

10.3390/molecules24152773 ◽

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.

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