scholarly journals Direct Decarboxylative Allylation and Arylation of Aliphatic Carboxylic Acids Using Flavin-Mediated Photoredox Catalysis

2019 ◽  
Vol 2020 (10) ◽  
pp. 1539-1550 ◽  
Author(s):  
Nieves P. Ramirez ◽  
Teresa Lana-Villarreal ◽  
Jose C. Gonzalez-Gomez
Keyword(s):  
Carboxylic Acids ◽  
Photoredox Catalysis ◽  
Decarboxylative Allylation ◽  
Aliphatic Carboxylic Acids

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.

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

scholarly journals Decarboxylative Fluorination of Aliphatic Carboxylic Acids via Photoredox Catalysis

2015 ◽  
Vol 137 (17) ◽  
pp. 5654-5657 ◽  
Author(s):  
Sandrine Ventre ◽  
Filip R. Petronijevic ◽  
David W. C. MacMillan
Keyword(s):  
Carboxylic Acids ◽  
Photoredox Catalysis ◽  
Aliphatic Carboxylic Acids

Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution

2016 ◽  
Vol 18 (9) ◽  
pp. 2188-2191 ◽  
Author(s):  
Lei Cui ◽  
He Chen ◽  
Chao Liu ◽  
Chaozhong Li
Keyword(s):  
Aqueous Solution ◽  
Carboxylic Acids ◽  
Decarboxylative Allylation ◽  
Aliphatic Carboxylic Acids

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.

Metal-Free Regioselective Alkylation of Imidazo[1,2-a]pyridines with N-Hydroxyphthalimide Esters under Organic Photoredox Catalysis

Synlett ◽  
2020 ◽  
Vol 31 (04) ◽  
pp. 363-368 ◽  
Author(s):  
Can Jin ◽  
Bin Sun ◽  
Tengwei Xu ◽  
Liang Zhang ◽  
Rui Zhu ◽  
...  
Keyword(s):  
Visible Light ◽  
Carboxylic Acids ◽  
Room Temperature ◽  
Eosin Y ◽  
Photoredox Catalysis ◽  
Mechanistic Studies ◽  
Metal Free ◽  
Regioselective Alkylation ◽  
Decarboxylative Coupling ◽  
Aliphatic Carboxylic Acids

A visible-light-induced direct C–H alkylation of imidazo[1,2-a]pyridines has been developed. It proceeds at room temperature by employing inexpensive Eosin Y as a photocatalyst and alkyl N-hydroxyphthalimide (NHP) esters as alkylation reagents. A variety of NHP esters derived from aliphatic carboxylic acids (primary, secondary, and tertiary) were tolerated in this protocol, giving the corresponding C-5-alkylated products in moderate to excellent yields. Mechanistic studies indicate that a radical decarboxylative coupling pathway was involved in this process.

Transition-metal-free visible-light photoredox catalysis at room-temperature for decarboxylative fluorination of aliphatic carboxylic acids by organic dyes

2015 ◽  
Vol 51 (59) ◽  
pp. 11864-11867 ◽  
Author(s):  
Xinxin Wu ◽  
Chunna Meng ◽  
Xiaoqian Yuan ◽  
Xiaotong Jia ◽  
Xuhong Qian ◽  
...  
Keyword(s):  
Transition Metal ◽  
Visible Light ◽  
Carboxylic Acids ◽  
Room Temperature ◽  
Organic Dyes ◽  
Photoredox Catalysis ◽  
Green Method ◽  
Metal Free ◽  
Aliphatic Carboxylic Acids

We report herein an efficient, general and green method for decarboxylative fluorination of aliphatic carboxylicacids.

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