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

Low-energy photoredox catalysis DOI
David C. Cabanero, Tomislav Rovis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

Language: Английский

Citations

10
Radical-polar Crossover Reaction of Glycine Derivatives DOI

Youwan Ye,

Xin Zhang,

Peng Kong

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(75), P. 10378 - 10381

Published: Jan. 1, 2024

Here we report a visible-light facilitated radical addition strategy for the preparation of various natural or unnatural α-amino acids from readily available glycine derivatives and alkenes. A key aspect in achieving this side carbon chain introduction reaction, while circumventing well-documented cyclization pathway, was employment radical-polar crossover under redox neutral conditions.

Language: Английский

Citations

5
Radical approaches for C(sp3)–N bond cleavage in deaminative transformations DOI
J. Kim,

Eun Song Lim,

Ji Yeon Park

et al.

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

Published: Jan. 1, 2025

This review summarizes recent advancements in radical-mediated deaminative transformations, focusing on the mechanisms, substrate compatibility, and emerging applications synthetic organic chemistry.

Language: Английский

Citations

0
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
Visible-Light-Mediated Nucleophilic Addition of Alkene with Aldehyde: Synthesis of Secondary Alcohols DOI

D. Hu,

Huu Phuong Dang,

Zhen Liang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 10, 2024

Herein, a photocatalytic strategy for the synthesis of secondary alcohols by nucleophilic addition an alkene with aldehyde is described. This operationally simple methodology opens approach using commercially available reagents in moderate to excellent yields. Mechanistic studies indicate that formation radical anion from via single-electron transfer key step this reaction.

Language: Английский

Citations

2
(2 + 2 + 1)-Cyclization of Glycine Derivatives with Alkenes and CO2 DOI

Youwan Ye,

Congde Huo

Organic Letters, Journal Year: 2024, Volume and Issue: 26(37), P. 7897 - 7901

Published: Sept. 5, 2024

A highly atom-economic (2 + 2 1)-cyclization of glycine derivatives with alkenes and CO

Language: Английский

Citations

1
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
Photomediated Deaminative Generation of Tertiary Anions DOI
Dirk Trauner, Andreas Hess

Synfacts, Journal Year: 2024, Volume and Issue: 20(03), P. 0322 - 0322

Published: Feb. 14, 2024

Key words photocatalysis - carbanions cross-coupling

Language: Английский

Citations

0
Reductive deaminative cross-coupling of alkyl bistriflimides enabled by electrocatalysis DOI Creative Commons
Xiangzhang Tao, Wooseok Lee,

Zhimin Xu

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(47)

Published: Nov. 22, 2024

We present a versatile nickel-electrocatalytic deaminative cross-coupling platform for the efficient construction of C(sp 3 )–C(sp ) and 2 bonds from readily available alkyl bistriflimides. This methodology involves assembly two leaving groups on amines to form bistriflimides, followed by their effective coupling with wide range halides, pseudohalides, aryl alkenyl halides under electrochemical reductive conditions. Moreover, successful application relay transition metal–free cross-electrophile further demonstrates versatility bistriflimides as valuable building blocks in organic synthesis. Combined control experiments density functional theory calculations provide insights into reaction pathway crucial role iodide catalytic process.

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