Photoredox‐Catalyzed Decarboxylation of Oxetane‐2‐Carboxylic Acids Initiated by Oxidation of DIPEA DOI
Elvis C. McFee, Katie A. Rykaczewski, Corinna S. Schindler

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Abstract Oxetanes are valuable motifs in medicinal chemistry applications, with demonstrated potential to serve as bioisosteres for an array of functional groups. Through the visible‐light‐mediated photoredox hydrodecarboxylation 2‐aryl oxetane 2‐carboxylic acids this work enables access products a [2+2]‐photocycloaddition between alkenes and aryl aldehydes without challenges associated traditional UV‐light‐mediated Paternò‐Büchi reaction. Investigation into mechanism reveals substrate‐dependent modes initiation under conditions reported herein. Divergence diastereomeric outcome is observed, mechanistic probes elucidating key hydrogen‐bonding steric interactions.

Language: Английский

Simplified Modular Access to Enantiopure 1,2-Aminoalcohols via Ni-Electrocatalytic Decarboxylative Arylation DOI Creative Commons

Jiawei Sun,

Hirofumi Endo,

Megan A. Emmanuel

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6209 - 6216

Published: Feb. 22, 2024

Chiral aminoalcohols are omnipresent in bioactive compounds. Conventional strategies to access this motif involve multiple-step reactions install the requisite functionalities stereoselectively using conventional polar bond analysis. This study reveals that a simple chiral oxazolidine-based carboxylic acid can be readily transformed substituted with high stereochemical control by Ni-electrocatalytic decarboxylative arylation. general, robust, and scalable coupling used synthesize variety of medicinally important compounds, avoiding protecting functional group manipulations, thereby dramatically simplifying their preparation.

Language: Английский

Citations

14

A Unified Method for Oxidative and Reductive Decarboxylative Arylation with Orange Light-Driven Ir/Ni Metallaphotoredox Catalysis DOI

Katherine A. Xie,

Eva Bednářová, Candice L. Joe

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25780 - 25787

Published: Sept. 5, 2024

Carboxylic acids and their derivatives are powerful building blocks in dual Ir/Ni metallaphotoredox methods of decarboxylative arylation due to abundance as feedstock compounds. However, the library accessible carboxylic is limited by trends radical stability, often necessitating development specific systems for challenging substrates. Herein, we disclose application a new Ir(III) photocatalyst low-energy orange light system with broad applicability activating both native redox-active esters (RAEs). This method represents first known example complementary oxidative reductive paradigms broadly similar reaction conditions, unlocking reactivity We further show wide scope aryl halide acid coupling partners regimes, added advantages over blue-light-catalyzed alkylation photosensitive

Language: Английский

Citations

5

Unlocking Tertiary Acids for Metallaphotoredox C(sp2)–C(sp3) Decarboxylative Cross-Couplings DOI
Junqing Guo,

Derek Norris,

Antonio Ramı́rez

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 11910 - 11918

Published: Aug. 25, 2023

Dual nickel photoredox catalysis conditions have been developed for the decarboxylative cross-coupling of aryl halides and carboxylic acids containing fully substituted α-carbons, a valuable but challenging substrate class C(sp2)–C(sp3) bond-forming reactions. High-throughput experimentation identified Ni(TMHD)2 as optimal precatalyst this reaction in contrast to nickel-bipyridyl complexes typically employed couplings, which predominantly furnished undesired C–O products. Computational work provides insight into potential mechanistic underpinnings C–C vs selectivity nickel-diketonate complex.

Language: Английский

Citations

12

Graphitic Carbon Nitride as a Photocatalyst for Decarboxylative C(sp2)–C(sp3) Couplings via Nickel Catalysis DOI Creative Commons
Florian Lukas, Michael T. Findlay, Méritxell Fillols

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 29, 2024

The development of robust and reliable methods for the construction C(sp

Language: Английский

Citations

4

Photoredox Catalysis DOI
Geraint H. M. Davies, Patricia Z. Musacchio, Trevor C. Sherwood

et al.

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0

Green Synthesis of Morpholines via Selective Monoalkylation of Amines DOI Creative Commons
Kacey G. Ortiz, Andrew T. Brusoe, Jason An

et al.

Published: Aug. 30, 2024

Morpholines are common heterocycles in pharmaceutical and agricultural products, yet methods to synthesize them from 1,2-amino alcohols inefficient. We report the simple, high yielding, one or two-step, redox neutral protocol using inexpensive reagents (ethylene sulfate tBuOK) for conversion of morpholines. Key this methodology is identification general conditions that allow clean isolation monoalkylation products derived a simple SN2 reaction between an amine ethylene sulfate. Experiments suggest degree selectivity dependent upon structure reacting alcohol as well unique properties This method can be used synthesis variety morpholines containing substituents at various positions, including 28 examples primary amines multiple contained known active ingredients. have conducted on >50 g scale. also demonstrated formal morpholine Overall, while new has many environmental safety benefits relative traditional prepare most striking feature facile selective amines. explored reactions beyond those related morpholines, obtaining proof-of-principle piperazines 2-carbon electrophile fragment couplings.

Language: Английский

Citations

1

Green Synthesis of Morpholines via Selective Monoalkylation of Amines DOI
Kacey G. Ortiz, Andrew T. Brusoe, Jason An

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Morpholines are common heterocycles in pharmaceutical and agricultural products, yet methods to synthesize them from 1,2-amino alcohols inefficient. We report the simple, high yielding, one or two-step, redox neutral protocol using inexpensive reagents (ethylene sulfate

Language: Английский

Citations

1

Unlocking Tertiary Acids for Metallaphotoredox C(sp2)-C(sp3) Decarboxylative Cross-Couplings DOI Creative Commons
Junqing Guo,

Derek Norris,

Antonio Ramı́rez

et al.

Published: June 19, 2023

Dual nickel photoredox catalysis conditions have been developed for the decarboxylative cross-coupling of aryl halides and carboxylic acids containing fully substituted alpha carbons, a valuable but challenging substrate class C(sp2)–C(sp3) bond-forming reactions. High-throughput experimentation identified Ni(TMHD)2 as optimal precatalyst this reaction in contrast to nickel-bipyridyl complexes typically employed couplings, which predominantly furnished undesired C–O products. Computational work provides insight into potential mechanistic underpinnings C–C vs. selectivity nickel-diketonate complex.

Language: Английский

Citations

3

Graphitic Carbon Nitride as a Photocatalyst for Decarboxylative C(sp2)–C(sp3) Couplings via Nickel Catalysis DOI Creative Commons
Florian Lukas, Michael T. Findlay, Méritxell Fillols

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: May 29, 2024

Abstract The development of robust and reliable methods for the construction C(sp 2 )−C(sp 3 ) bonds is vital accessing an increased array structurally diverse scaffolds in drug discovery campaigns. While significant advances towards this goal have been achieved using metallaphotoredox chemistry, many these utilise photocatalysts based on precious‐metals due to their efficient redox processes tuneable properties. However, cost, scarcity, toxicity metals, search suitable replacements should be a priority. Here, we show use commercially available heterogeneous semiconductor graphitic carbon nitride (gCN) as photocatalyst, combined with nickel catalysis, cross‐coupling between aryl halide carboxylic acid coupling partners. gCN has shown engage single‐electron‐transfer (SET) energy‐transfer (EnT) formation C−X bonds, manuscript overcome previous limitations furnish C−C over C−O acids. A broad scope both halides acids presented, recycling photocatalyst demonstrated. mechanism reaction also investigated.

Language: Английский

Citations

0

Photoredox‐Catalyzed Decarboxylation of Oxetane‐2‐Carboxylic Acids Initiated by Oxidation of DIPEA DOI
Elvis C. McFee, Katie A. Rykaczewski, Corinna S. Schindler

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Abstract Oxetanes are valuable motifs in medicinal chemistry applications, with demonstrated potential to serve as bioisosteres for an array of functional groups. Through the visible‐light‐mediated photoredox hydrodecarboxylation 2‐aryl oxetane 2‐carboxylic acids this work enables access products a [2+2]‐photocycloaddition between alkenes and aryl aldehydes without challenges associated traditional UV‐light‐mediated Paternò‐Büchi reaction. Investigation into mechanism reveals substrate‐dependent modes initiation under conditions reported herein. Divergence diastereomeric outcome is observed, mechanistic probes elucidating key hydrogen‐bonding steric interactions.

Language: Английский

Citations

0