Biocatalytic Formal Asymmetric para-Aminoethylation of Unprotected Phenols to Chiral Amines DOI
Jingqi Zhang, Xuan Deng, Xue Han

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 81 - 90

Published: Dec. 13, 2024

Enantiomerically pure amines are vital for the development of biologically active compounds in medicine and agriculture. While aminoalkylation phenols is well-established creating nitrogen-containing frameworks, regio- stereoselective para-aminoethylation unprotected underexplored. To fill this gap, we propose a one-pot cascade biocatalysis system asymmetric into chiral amines, using simple pyruvate, NH4Cl, D/l-alanine as starting materials. Utilizing modular approach, successfully performed through sequential process vinylation hydroamination, achieving good conversions (51.0–72.0%) >99% ee both enantiomers amines. Additionally, biobased p-hydroxycinnamic acid l-tyrosine their derivatives were converted with moderate to (39.4–87%) integrating decarboxylation/hydroamination deamination-decarboxylation/hydroamination. This marks successful de novo biosynthesis method formal phenols.

Language: Английский

Novel Azo dyes containing a hydrazide-hydrazone moiety for dyeing polyester fabric DOI Creative Commons
Ali A. Ali,

Mostafa A. Ismail,

Walid E. Elgammal

et al.

Scientific Reports, Journal Year: 2025, Volume and Issue: 15(1)

Published: Feb. 5, 2025

Language: Английский

Citations

1
Visible-Light-Induced Synthesis of Esters via a Self-Propagating Radical Reaction DOI

Zelin Zhao,

Wenping Li,

Qiujie Shan

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 90(4), P. 1616 - 1627

Published: Jan. 16, 2025

We herein disclose a visible-light-induced synthesis of O-aryl esters through the cross-dehydrogenative coupling aldehydes with phenols using BrCCl3, in which phenolate functions as both substrate and photosensitizer. This transition-metal- photocatalyst-free esterification is suitable for wide range substrates gives moderate to excellent yields (up 95%). Mechanistic studies provided evidence self-propagating radical reaction involving homolytic cleavage aldehydic C–H bond formation acyl bromides. BrCCl3 serves an oxidant hydrogen atom transfer (HAT) agent.

Language: Английский

Citations

0
Cesium and Phenoxide Interaction Enabled by Rh Overrides the Innate Solvent-Mediated Chemoselectivity DOI

Romin Gogoi,

Garima Jindal

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12351 - 12358

Published: Aug. 5, 2024

DLPNO-CCSD(T) calculations are carried out to understand the distinctive chemoselectivity in a Rh(II)-catalyzed carbene insertion into C(sp2)–H bond unprotected phenols without preinstalled directing groups. As per conventional rules of solvation and separated ion pair polar aprotic solvents like acetonitrile, reaction should have resulted an O–H insertion. However, our reveal transition state model that helps overriding innate acetonitrile. It involves explicit participation added Cs2CO3 base, where interaction between phenoxide oxygen Cs cation, but not as metal-bound phenoxide, is crucial for controlling chemoselectivity. Our study will be helpful developing further reactions with broad catalyst, substrate, solvent scope.

Language: Английский

Citations

0
Late-Stage Radical C–H Alkylamination of Tyrosine Compounds and Phenol-Containing Drugs DOI
Paula Andrade‐Sampedro, Arkaitz Correa

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

Published: Oct. 3, 2024

A modular site-selective iron-catalyzed radical amination of a number phenol-containing biomolecules such as tyrosine-containing peptides, estrogens, and other phenol-based pharmaceuticals has been developed. The method features the use cost-efficient combination FeBr

Language: Английский

Citations

0
C–H acylation as an enabling tool to tag phenolic drugs DOI Creative Commons
Carlota Girón-Elola, Arkaitz Correa

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A Pd-catalyzed directed C–H acylation of a collection intricate phenol-containing compounds with ethanol and other alcohols aldehydes is reported.

Language: Английский

Citations

0
Biocatalytic Formal Asymmetric para-Aminoethylation of Unprotected Phenols to Chiral Amines DOI
Jingqi Zhang, Xuan Deng, Xue Han

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 81 - 90

Published: Dec. 13, 2024

Enantiomerically pure amines are vital for the development of biologically active compounds in medicine and agriculture. While aminoalkylation phenols is well-established creating nitrogen-containing frameworks, regio- stereoselective para-aminoethylation unprotected underexplored. To fill this gap, we propose a one-pot cascade biocatalysis system asymmetric into chiral amines, using simple pyruvate, NH4Cl, D/l-alanine as starting materials. Utilizing modular approach, successfully performed through sequential process vinylation hydroamination, achieving good conversions (51.0–72.0%) >99% ee both enantiomers amines. Additionally, biobased p-hydroxycinnamic acid l-tyrosine their derivatives were converted with moderate to (39.4–87%) integrating decarboxylation/hydroamination deamination-decarboxylation/hydroamination. This marks successful de novo biosynthesis method formal phenols.

Language: Английский

Citations

0