Photoredox catalysis enabled alkylation of alkenyl carboxylic acids with N-(acyloxy)phthalimide via dual decarboxylation

Under mild condition, redox-active esters of carboxylic acids reacted with aryl and alkyl substituted alkynes in good yields. A copper-acetylid-ligand is a key intermediate for constructing C(sp)–C(sp3) bond.

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Quaternary Centers via Ni-Catalyzed Cross-Coupling of Tertiary Carboxylic Acids and Aryl Zinc Reagents

10.26434/chemrxiv.7499288 ◽

2018 ◽

Author(s):

Phil Baran ◽

Pavel Mykhailiuk ◽

haolin zhang ◽

Rohan R. Merchant ◽

Courtney A. Smith ◽

...

Keyword(s):

Carboxylic Acids ◽

Cross Coupling ◽

Simple Method ◽

Quaternary Centers ◽

Active Esters ◽

Redox Active ◽

The Cross

<div> <div> <div> <p>This work bridges a gap in the cross-coupling of aliphatic redox-active esters with aryl zinc reagents. Previously limited to primary, secondary and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using Ni-catalysis. The scope of this operationally simple method is broad and can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers. </p> </div> </div> </div>

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Photoinduced copper-catalyzed dual decarboxylative coupling of α,β-unsaturated carboxylic acids with redox-active esters

Tetrahedron ◽

10.1016/j.tet.2021.132259 ◽

2021 ◽

pp. 132259

Author(s):

Xiao-Yu Lu ◽

Yang Gao ◽

Qi-Le Liu ◽

Ze-Jie Xia

Keyword(s):

Carboxylic Acids ◽

Active Esters ◽

Redox Active ◽

Decarboxylative Coupling ◽

Unsaturated Carboxylic Acids

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Quaternary Centers via Ni-Catalyzed Cross-Coupling of Tertiary Carboxylic Acids and Aryl Zinc Reagents

10.26434/chemrxiv.7499288.v1 ◽

2018 ◽

Author(s):

Phil Baran ◽

Pavel Mykhailiuk ◽

haolin zhang ◽

Rohan R. Merchant ◽

Courtney A. Smith ◽

...

Keyword(s):

Carboxylic Acids ◽

Cross Coupling ◽

Simple Method ◽

Quaternary Centers ◽

Active Esters ◽

Redox Active ◽

The Cross

<div> <div> <div> <p>This work bridges a gap in the cross-coupling of aliphatic redox-active esters with aryl zinc reagents. Previously limited to primary, secondary and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using Ni-catalysis. The scope of this operationally simple method is broad and can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers. </p> </div> </div> </div>

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Nucleophilic (Radio)Fluorination of Redox-Active Esters via Radical-Polar Crossover Enabled by Photoredox Catalysis

Journal of the American Chemical Society ◽

10.1021/jacs.0c03125 ◽

2020 ◽

Vol 142 (20) ◽

pp. 9493-9500 ◽

Cited By ~ 8

Author(s):

Eric W. Webb ◽

John B. Park ◽

Erin L. Cole ◽

David J. Donnelly ◽

Samuel J. Bonacorsi ◽

...

Keyword(s):

Photoredox Catalysis ◽

Active Esters ◽

Redox Active

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

10.26434/chemrxiv.6349253 ◽

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.

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