Visible-light-induced Markovnikov addition of olefin for construction of deuterated α-tertiary amino acid derivatives DOI
Rui Chen, Cong Lu, Yujun Li

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3427 - 3435

Published: Jan. 1, 2024

An efficient photoredox system was reported for construction of deuterated α-tertiary amino acid derivatives through the Markovnikov addition olefins.

Language: Английский

Synergistic Photoenzymatic Catalysis Enables Synthesis of a-Tertiary Amino Acids Using Threonine Aldolases DOI

Yao Ouyang,

Claire G. Page,

Catherine Bilodeau

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 13754 - 13759

Published: May 13, 2024

a-Tertiary amino acids are essential components of drugs and agrochemicals, yet traditional syntheses step-intensive provide access to a limited range structures with varying levels enantioselectivity. Here, we report the α-alkylation unprotected alanine glycine by pyridinium salts using pyridoxal (PLP)-dependent threonine aldolases Rose Bengal photoredox catalyst. The strategy efficiently prepares various a-tertiary in single chemical step as enantiomer. UV–vis spectroscopy studies reveal ternary interaction between salt, protein, photocatalyst, which hypothesize is responsible for localizing radical formation active site. This method highlights opportunity combining catalysts enzymes new catalytic functions known enzymes.

Language: Английский

Citations

19
Cobalt‐Catalyzed Asymmetric Aza‐Nozaki–Hiyama–Kishi (NHK) Reaction of α‐Imino Esters with Alkenyl Halides DOI

Tingting Xia,

Yinhui Wu,

Jiangtao Hu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(7)

Published: Jan. 2, 2024

Chromium-catalyzed enantioselective Nozaki-Hiyama-Kishi (NHK) reaction represents one of the most powerful approaches for formation chiral carbon-heteroatom bond. However, construction sterically encumbered tetrasubstituted stereocenter through NHK still posts a significant challenge. Herein, we disclose cobalt-catalyzed aza-NHK ketimine with alkenyl halide to provide convenient synthetic approach manufacture enantioenriched α-vinylic amino acid. This protocol exhibits excellent functional group tolerance 99 % ee in cases. Additionally, this asymmetric reductive method is also applicable aldimine access trisubstituted stereogenic centers.

Language: Английский

Citations

18
Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis DOI

Xiang‐Kui He,

Liang‐Qiu Lu,

Bao-Ru Yuan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

Citations

17
Stereodivergent access to non-natural α-amino acids via enantio- and Z / E -selective catalysis DOI
Panpan Li, Zheng En, Guanlin Li

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6712), P. 972 - 979

Published: Aug. 29, 2024

The precise control of

Language: Английский

Citations

12
Chromium‐ and Metal‐Reductant‐Free Asymmetric Nozaki–Hiyama–Kishi (NHK) Reaction Enabled by Metallaphotoredox Catalysis DOI

Pei Gu,

Linlin Ding,

Xiaowu Fang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(37)

Published: June 25, 2024

Abstract Chiral allylic alcohols are highly prized in synthetic chemistry due to their versatile reactivity stemming from both alkenyl and hydroxyl functionalities. While the Nozaki–Hiyama–Kishi (NHK) reaction is a widely used method for synthesis of alcohols, it suffers drawbacks such as use toxic chromium salts, high amounts metal reductants, poor enantiocontrol. To address these limitations, we present novel approach involving metallaphotoredox‐catalyzed asymmetric NHK production chiral alcohols. This marries (pseudo)halides with aldehydes, leveraging synergistic blend nickel catalyst photocatalyst. innovative technique enables oxidative addition insertion just using nickel, diverging significantly conventional pathway mediated by salts. The adoption this methodology holds immense promise crafting spectrum intricate compounds, particularly those significance pharmaceuticals. Detailed experimental investigations have shed light on metallaphotoredox process, further enhancing our understanding enabling advancements.

Language: Английский

Citations

5
Acid-Catalyzed Highly Enantioselective Synthesis of α-Amino Acid Derivatives from Sulfinamides and Alkynes DOI
Herui Liu,

Guangwu Sun,

Yuchao Zhang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1601 - 1606

Published: Feb. 19, 2024

An enantioselective difunctionalization of activated alkynes using chiral sulfinamide reagents is developed. It an atom and chirality transfer process that allows for the modular synthesis optically active α-amino acid derivatives under mild conditions. The reaction proceeds through acid-catalyzed [2,3]-sigmatropic rearrangement mechanism with predictable stereochemistry a broad scope.

Language: Английский

Citations

4
CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8888 - 8895

Published: Jan. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Language: Английский

Citations

4
Biocatalytic Synthesis of α-Amino Esters via Nitrene C–H Insertion DOI
Edwin Alfonzo,

Deirdre Hanley,

Zi‐Qi Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(40), P. 27267 - 27273

Published: Sept. 27, 2024

α-Amino esters are precursors to noncanonical amino acids used in developing small-molecule therapeutics, biologics, and tools chemical biology. α-C-H amination of abundant inexpensive carboxylic acid through nitrene transfer presents a direct approach α-amino esters. Methods for nitrene-mediated the protic bonds esters, however, underdeveloped. This gap arises because hydrogen atom abstraction (HAA) C-H by electrophilic metal-nitrenoids is slow: preferentially react with polarity-matched, hydridic bonds, even when weaker present. study describes discovery evolution highly stable protoglobin transferases that catalyze enantioselective intermolecular We developed high-throughput assay evaluate activity enantioselectivity mutant enzymes together their sequences using Every Variant Sequencing (evSeq) method. The enabled identification enantiodivergent function at ambient conditions

Language: Английский

Citations

4
Research Progress in the Synthesis of α-Tertiary Amines via Radical Strategies DOI

Jia‐Heng Fang,

Run Tian,

Ji‐Jun Chen

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 22 - 22

Published: Jan. 1, 2025

Language: Английский

Citations

0
Gold-modified nanoporous silicon for photoelectrochemical regulation of intracellular condensates DOI

Jing Zhang,

Pengju Li,

Jiping Yue

et al.

Nature Nanotechnology, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

Language: Английский

Citations

0