Photoredox Catalysis as a Strategy for CO 2 Incorporation: Direct Access to Carboxylic Acids from a Renewable Feedstock

2019 ◽  
Vol 58 (17) ◽  
pp. 5492-5502 ◽  
Author(s):  
Charles S. Yeung
Keyword(s):  
Carboxylic Acids ◽  
Direct Access ◽  
Photoredox Catalysis ◽  
Renewable Feedstock

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.

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.

scholarly journals Fast Carbon Isotope Exchange of Carboxylic Acids Enabled by Organic Photoredox Catalysis

2021 ◽  
Vol 143 (5) ◽  
pp. 2200-2206
Author(s):  
Duanyang Kong ◽  
Maxime Munch ◽  
Qiqige Qiqige ◽  
Christopher J. C. Cooze ◽  
Benjamin H. Rotstein ◽  
...  
Keyword(s):  
Carbon Isotope ◽  
Carboxylic Acids ◽  
Isotope Exchange ◽  
Photoredox Catalysis

scholarly journals Combined Photoredox and Carbene Catalysis for the Synthesis of Ketones from Carboxylic Acids

2020 ◽  
Author(s):  
Anna Davies ◽  
keegan fitzpatrick ◽  
Rick Betori ◽  
Karl Scheidt
Keyword(s):  
Carboxylic Acids ◽  
Late Stage ◽  
Pharmaceutical Compounds ◽  
Single Electron ◽  
Photoredox Catalysis ◽  
Radical Coupling ◽  
Electron Reduction

Disclosed herein is the development of a novel single-electron reduction of acyl azoliums for the formation of ketones from carboxylic acids. Facile construction of the acyl azolium <i>in situ</i> followed by a radical-radical coupling was made possible using merged NHC-photoredox catalysis. The utility of this protocol in synthesis was demonstrated in the late-stage functionalization of a variety of pharmaceutical compounds.

ChemInform Abstract: Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis.

ChemInform ◽  
2015 ◽  
Vol 46 (42) ◽  
pp. no-no
Author(s):  
Sandrine Ventre ◽  
Filip R. Petronijevic ◽  
David W. C. MacMillan
Keyword(s):  
Carboxylic Acids ◽  
Photoredox Catalysis ◽  
Aliphatic Carboxylic Acids

Dichloromethane as a methylene synthon for regioselective linkage of diverse carboxylic acids: Direct access to methylene diesters under metal-free conditions

2019 ◽  
Vol 30 (6) ◽  
pp. 1173-1177 ◽  
Author(s):  
Shuiliang Wang ◽  
Zhengjiang Fu ◽  
Zhicong Huang ◽  
Yongqing Jiang ◽  
Shengmei Guo ◽  
...  
Keyword(s):  
Carboxylic Acids ◽  
Direct Access ◽  
Metal Free

ChemInform Abstract: Room Temperature Decarboxylative Trifluoromethylation of α,β-Unsaturated Carboxylic Acids by Photoredox Catalysis.

ChemInform ◽  
2014 ◽  
Vol 45 (24) ◽  
pp. no-no
Author(s):  
Pan Xu ◽  
Ablimit Abdukader ◽  
Kaidong Hu ◽  
Yixiang Cheng ◽  
Chengjian Zhu
Keyword(s):  
Carboxylic Acids ◽  
Room Temperature ◽  
Photoredox Catalysis ◽  
Unsaturated Carboxylic Acids
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