Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps DOI Creative Commons

Ruijie Mi,

Rong-Kai Wu,

Jierui Jing

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(48)

Published: Nov. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Language: Английский

Paired Electrolysis Enabled Remote Amino Alcohols Synthesis DOI
Haonan Zhang, Kun Xu

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 722 - 722

Published: Jan. 1, 2025

Language: Английский

Citations

0
Rhodium- and Iridium-Catalyzed (Enantioselective) Fluoroamidation of gem-Difluoroalkenes via Chelation Assistance DOI
Heng Song,

Ruijie Mi,

Xingwei Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6555 - 6562

Published: April 7, 2025

Language: Английский

Citations

0
Paired Electro‐Synthesis of Remote Amino Alcohols with/in H2O DOI Open Access
Zhixiong Ruan,

Xinyue Fang,

Xinwei Hu

et al.

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

Published: Nov. 13, 2024

Abstract Amino alcohols, particularly remote amino alcohols and peptide are valuable due to their functional diversity in biologically active compounds. However, traditional synthesis methods face significant challenges, making electrochemistry an attractive alternative. We have developed a mild biocompatible sequential paired electrolysis strategy, leveraging copper‐electrocatalysis synthesize diverse including unnatural alcohols. Both experimental results density theory (DFT) calculations demonstrated that water serves as both the hydroxyl source solvent, facilitating generation of CuH with Cu(I) at cathode, which turn reduces aldehyde intermediates formed during reaction.

Language: Английский

Citations

3
Efficient Access to Enantioenriched gem-Difluorinated Heterocycles via Silver-Catalyzed Asymmetric Cycloaddition Reaction DOI
Jun Liu, Lijun Xu, Xiaolong Yu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 7267 - 7276

Published: April 25, 2024

gem-Difluorinated alkenes represent versatile building blocks to divergently access functional molecules containing gem-difluorinated methyl groups; however, little advances have been made on the transformations of gem-difluoro-1,3-dienes, particularly for enantioselective versions. In this paper, we introduced an [4 + 2] cycloaddition gem-difluoro-1,3-butadienes with azodicarbonates catalyzed by AgSF6 and (S)-MOP at a low catalyst loading that enables generation enantioenriched hydropyridazine derivatives in high yields enantioselectivities (up 98% yield, ee). Control experiments DFT analysis revealed reactions probably undergo cascade reaction pathway, are activated chiral silver-(S)-MOP complex control reactions.

Language: Английский

Citations

3
Incorporating azaheterocycle functionality in intramolecular aerobic, copper-catalyzed aminooxygenation of alkenes DOI Creative Commons
Ethan M. DeCicco,

Neively Tlapale-Lara,

Shauna M. Paradine

et al.

RSC Advances, Journal Year: 2024, Volume and Issue: 14(39), P. 28822 - 28826

Published: Jan. 1, 2024

A key limitation across aminofunctionalizations is incompatibility with substrates bearing medicinally relevant N-heterocycles; in contrast, this aerobic, Cu-catalyzed aminooxygenation engages a diverse range of N-heterocycle-bearing substrates.

Language: Английский

Citations

0
Rh(III)-Catalyzed Alkene Anti Nucleoamidation to Access Diverse Heterocycles DOI

Noah Wagner-Carlberg,

Julia R. Dorsheimer, Tomislav Rovis

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(22), P. 17033 - 17038

Published: Nov. 4, 2024

Alkene difunctionalization methods are an attractive way to rapidly build molecular complexity by using readily available starting materials. One common approach is transition metal-catalyzed nucleometalation, which converts the C–C double bond a C–Nu and C–M bond. Commonly, tethered nucleophile used form pharmaceutically relevant heterocyclic cores in this manner. The resulting alkylmetal species can then be further functionalized number of ways. While exist aminate bond, direct installation valuable amides rare. Additionally, nucleometalation often limited use single type nucleophile. Herein, we disclose general method for Rh(III)-catalyzed nucleoamidation alkenes, forming variety cores.

Language: Английский

Citations

0
Paired Electro‐Synthesis of Remote Amino Alcohols with/in H2O DOI
Zhixiong Ruan,

Xinyue Fang,

Xinwei Hu

et al.

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

Published: Nov. 13, 2024

Abstract Amino alcohols, particularly remote amino alcohols and peptide are valuable due to their functional diversity in biologically active compounds. However, traditional synthesis methods face significant challenges, making electrochemistry an attractive alternative. We have developed a mild biocompatible sequential paired electrolysis strategy, leveraging copper‐electrocatalysis synthesize diverse including unnatural alcohols. Both experimental results density theory (DFT) calculations demonstrated that water serves as both the hydroxyl source solvent, facilitating generation of CuH with Cu(I) at cathode, which turn reduces aldehyde intermediates formed during reaction.

Language: Английский

Citations

0
Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps DOI Creative Commons

Ruijie Mi,

Rong-Kai Wu,

Jierui Jing

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(48)

Published: Nov. 27, 2024

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.

Language: Английский

Citations

0