Recent Progress in the Photocatalytic Synthesis of α‐Tertiary Primary Amines DOI

Xianzhou Zheng,

Weiming Yuan

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(40)

Published: May 31, 2024

Abstract α ‐Tertiary primary amines ( ‐TPAs) bearing a fully substituted carbon center adjacent to the N ‐unsubstituted amino group (−NH 2 ) exhibit unique biochemical and physicochemical activities. While due sterically congested structure strong nucleophilic alkaline natures of these amine compounds, their facile synthesis remains an inherent challenge. Traditional methods commonly rely on tedious ‐protection/deprotection operations highly reactive organometallic reagents, thus leading poor atom step‐economy limited functional compatibility. Modern photoredox catalysis offers robust tool prepare such structurally synthetically valuable architectures via radical pathway under extremely mild conditions. In this review, recent progress in photocatalytic ‐TPAs is systematically reviewed, reaction scope, limitations, mechanisms for reactions are discussed.

Language: Английский

Chemodivergent dearomatization of benzene-linked O-oxime esters via EnT-induced radical cross-coupling DOI Creative Commons
Guohui Zeng,

Dongwen Guo,

Huanfeng Jiang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Radical-mediated dearomatization strategies offer a blueprint for building value-added and synthetically valuable three-dimensional skeletons from readily available aromatic starting materials.

Language: Английский

Citations

0
Photocatalytic α-aminoalkyl radical addition of amines mediated by benzophenone under visible light DOI

Jinke Chen,

Qizhou Lian,

Xinru Jiang

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(9), P. 5471 - 5476

Published: Jan. 1, 2024

The photocatalytic α-aminoalkyl radical addition of amines faciliated by benzophenone is disclosed. This an example a alkylation method that uses low-toxicity solvents and mild reaction conditions.

Language: Английский

Citations

2
Modular Synthesis of Dehydroprolines by an Energy‐Transfer Enabled Cloke‐Wilson Rearrangement DOI
Austin D. Marchese, Tomislav Rovis

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

Published: Dec. 4, 2024

Abstract A one‐pot photocatalytic method is reported for the generation of dehydroprolines, valuable precursors to 5‐aryl prolines. Imines, obtained via simple condensation aminocyclopropane carboxylates (ACPC) with a broad range aldehydes, were employed in this transformation without purification. We demonstrate energy‐transfer (EnT) enabled Cloke‐Wilson‐type rearrangement affords both rare 1,2‐dehydroprolines or more thermodynamically favored 1,5‐isomers up >20 : 1 selectivity directions, using an identical catalytic system from same starting material. Syntheses intermediates bioactive molecules high yields and highlight enabling transformation. Mechanistic studies support proposed triplet‐triplet EnT mode activation, distinct previously developed singlet excited states accessed UV excitation.

Language: Английский

Citations

1
Cu‐UiO‐66 Catalyzed Synthesis of Imines via Acceptorless Dehydrogenative Coupling of Alcohols and Amines DOI

Yujuan Wu,

Qiang Zhu, Hongyang Xu

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 4, 2024

Abstract Herein, the Cu‐UiO‐66 catalyst was developed for acceptorless dehydrogenative coupling (ADC) between alcohols and amines to produce imines. The synthesized by installing Cu 2+ onto Zr‐oxo clusters in UiO‐66, efficiently catalyzes ADC reaction under mild environmentally friendly conditions with excellent selectivity. Mechanistic studies reveal that O 2 ⋅ − radicals porosity of formed participate cooperatively during catalytic cycle. Meanwhile, only by‐product system is benign water. Cycling tests hot filtration showed exhibited stability activity reaction. Importantly, might provide a promising strategy

Language: Английский

Citations

0
Modular Synthesis of Dehydroprolines by an Energy‐Transfer Enabled Cloke‐Wilson Rearrangement DOI
Austin D. Marchese, Tomislav Rovis

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

Published: Dec. 4, 2024

Abstract A one‐pot photocatalytic method is reported for the generation of dehydroprolines, valuable precursors to 5‐aryl prolines. Imines, obtained via simple condensation aminocyclopropane carboxylates (ACPC) with a broad range aldehydes, were employed in this transformation without purification. We demonstrate energy‐transfer (EnT) enabled Cloke‐Wilson‐type rearrangement affords both rare 1,2‐dehydroprolines or more thermodynamically favored 1,5‐isomers up >20 : 1 selectivity directions, using an identical catalytic system from same starting material. Syntheses intermediates bioactive molecules high yields and highlight enabling transformation. Mechanistic studies support proposed triplet‐triplet EnT mode activation, distinct previously developed singlet excited states accessed UV excitation.

Language: Английский

Citations

0
Recent advances in photoorganocatalysis (2019–2023) DOI
Petros L. Gkizis, Christoforos G. Kokotos

Royal Society of Chemistry eBooks, Journal Year: 2024, Volume and Issue: unknown, P. 199 - 236

Published: Dec. 18, 2024

From 2008 until now, the advent of photochemistry has offered a plethora synthetic opportunities to chemists worldwide. The ability light generate reactive species under mild reaction conditions provided access unexplored pathways. Lately, development photochemical reactions employing small organic molecules as catalysts increased. Serving basic principles Green Chemistry, have proven be an excellent alternative use metal-based complexes, performing elegant transformations. Their is based on their mediate events, such Single Electron Transfer (SET), Energy (EnT) and Hydrogen Atom (HAT). Furthermore, there been reports capability form Donor–Acceptor (EDA) complexes facilitating challenging Herein, we will focus promoted by during last 5 years (2019–2023).

Language: Английский

Citations

0
Recent Progress in the Photocatalytic Synthesis of α‐Tertiary Primary Amines DOI

Xianzhou Zheng,

Weiming Yuan

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(40)

Published: May 31, 2024

Abstract α ‐Tertiary primary amines ( ‐TPAs) bearing a fully substituted carbon center adjacent to the N ‐unsubstituted amino group (−NH 2 ) exhibit unique biochemical and physicochemical activities. While due sterically congested structure strong nucleophilic alkaline natures of these amine compounds, their facile synthesis remains an inherent challenge. Traditional methods commonly rely on tedious ‐protection/deprotection operations highly reactive organometallic reagents, thus leading poor atom step‐economy limited functional compatibility. Modern photoredox catalysis offers robust tool prepare such structurally synthetically valuable architectures via radical pathway under extremely mild conditions. In this review, recent progress in photocatalytic ‐TPAs is systematically reviewed, reaction scope, limitations, mechanisms for reactions are discussed.

Language: Английский

Citations

0