Organometallic Photocatalyst‐Promoted Synthesis and Modification of Carbohydrates under Photoirradiation DOI Open Access
Jing Wang,

Fan Zhou,

Yu‐Ping Xu

et al.

The Chemical Record, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 27, 2024

Carbohydrates are natural, renewable, chemical compounds that play crucial roles in biological systems. Thus, efficient and stereoselective glycosylation is an urgent task for the preparation of pure structurally well-defined carbohydrates. Photoredox catalysis has emerged as a powerful tool carbohydrate chemistry, providing alternative addressing some challenges glycochemistry. Over last few decades, Ir- Ru-based organometallic photocatalysts have attracted significant interest because their high stability, high-energy triplet state, strong visible-light absorption, long luminescence lifetime, amenability to ligand modification. This review highlights recent progress photocatalyst-promoted synthesis modification carbohydrates under photoirradiation, well related benefits drawbacks.

Language: Английский

Alcohol-alcohol cross-coupling enabled by S H 2 radical sorting DOI
Ruizhe Chen, Nicholas E. Intermaggio, Jiaxin Xie

et al.

Science, Journal Year: 2024, Volume and Issue: 383(6689), P. 1350 - 1357

Published: March 21, 2024

Alcohols represent a functional group class with unparalleled abundance and structural diversity. In an era of chemical synthesis that prioritizes reducing time to target maximizing exploration space, harnessing these building blocks for carbon-carbon bond-forming reactions is key goal in organic chemistry. particular, leveraging single activation mode form new C(sp

Language: Английский

Citations

49
Development of a General Organophosphorus Radical Trap: Deoxyphosphonylation of Alcohols DOI
Noah B. Bissonnette, Niels Bisballe, Andrew V. Tran

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7942 - 7949

Published: March 12, 2024

Here we report the design of a general, redox-switchable organophosphorus alkyl radical trap that enables synthesis broad range C(sp3)–P(V) modalities. This "plug-and-play" approach relies upon in situ activation alcohols and O═P(R2)H motifs, two broadly available inexpensive sources molecular complexity. The mild, photocatalytic deoxygenative strategy described herein allows for direct conversion sugars, nucleosides, complex pharmaceutical architectures to their analogs. includes facile incorporation medicinally relevant phosphonate ester prodrugs.

Language: Английский

Citations

23
Visible-light induced direct C(sp3)–H functionalization: recent advances and future prospects DOI
Jia‐Lin Tu, Yining Zhu, Pengcheng Li

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(18), P. 5278 - 5305

Published: Jan. 1, 2024

This review summarizes the latest methodological advances in photocatalytic C(sp 3 )–H functionalization, with a particular emphasis on formation of C–P, C–B, C–S bonds, etc ., and some prominent efforts asymmetric C–H functionalization.

Language: Английский

Citations

17
Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation DOI

Tanumoy Mandal,

Samrat Mallick,

Malekul Islam

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496

Published: Aug. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Language: Английский

Citations

10
Catalytic Phosphorylation of Tyrosine via a Radical Arbuzov Reaction DOI
Benjamin D. A. Shennan,

T Fukuta,

Mina Yamane

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 11, 2025

Synthetic protein/peptide modification is a powerful strategy for the development of new therapeutics and tools chemical biology. Accordingly, synthetic variant biological tyrosine phosphorylation, cornerstone post-translational landscape, could find widespread application in study this fundamental biochemical signal. This work describes mechanistically novel, redox-neutral, photocatalytic phosphorylation reaction via radical Arbuzov-type mechanism. The proceeds with good selectivity di-, tri-, oligopeptides under mild conditions near neutral pH, tolerating potentially problematic functionality. As first reaction, represents major advance toward goal phosphorylation.

Language: Английский

Citations

2
Trivalent Phospha-Brook rearrangement enabled practical deoxygenative phosphonylation of carbonyls DOI Creative Commons
Xiaoqiang Wu,

Shanya Lu,

Wei Zhong

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 16, 2025

Brønsted base-mediated [1,2]-phospha-Brook rearrangements have garnered considerable attention for developing new methodologies and efficiently constructing complex molecular structures. However, the strict reliance on pentavalent phosphonates imposes strong limitations reaction types, mechanistic constraint also excludes involvement of trivalent phosphine in same pathway. In this study, we employ Lewis acid rather than base to shift charge transfer from previous O-P-C direction a P-C-O process. This orthogonal approach can undergo unprecedented C-O bond cleavage instead traditional C-P splitting enables deoxygenative phosphorylation carbonyl compounds under metal-free conditions rapid access various tertiary oxides. The demonstrates excellent substrate scope, remarkable functional group compatibility, operational simplicity, offering significantly enhanced atom-economy compared strategies. Additionally, detailed studies reveal an unusual oxygen atom crossover clearly elucidate mechanism acid-mediated phospha-Brook rearrangement. These insights further deepen understanding phosphorus chemistry pave way design related reactions.

Language: Английский

Citations

1
Photocatalytic C–P bond formation based on the reaction of carbon-centered radicals with phosphides DOI

Shiyi Zhao,

Yi-Yun Huang,

Shihao Deng

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4882 - 4894

Published: Jan. 1, 2024

This review focuses on the synthesis of C–P bonds using carbon-centered radicals with phosphorous compounds different valence states (P III , P V 4 ) under photocatalysis.

Language: Английский

Citations

6
Photochemical phosphorus-enabled scaffold remodeling of carboxylic acids DOI
Qiupeng Peng,

Meemie U. Hwang,

Ángel Rentería‐Gómez

et al.

Science, Journal Year: 2024, Volume and Issue: 385(6716), P. 1471 - 1477

Published: Sept. 26, 2024

The excitation of carbonyl compounds by light to generate radical intermediates has historically been restricted ketones and aldehydes; carboxylic acids have overlooked because high energy requirements low quantum efficiency. A successful activation strategy would necessitate a bathochromic shift in the absorbance profile, an increase triplet diradical lifetime, ease further functionalization. We present single-flask transformation acyl phosphonates that can access synthetically useful diradicals under visible or near-ultraviolet irradiation. use phosphorus circumvents unproductive Norrish type I processes, promoting selectivity enables hydrogen-atom transfer reactivity. Use this promotes efficient scaffold remodeling through various annulation, contraction, expansion manifolds.

Language: Английский

Citations

6
Facile synthesis of alkylphosphonates from 4-alkyl-1,4-dihydropyridines via photoinduced formal deformylative phosphonylation DOI

Huan Zhang,

Zhonghe Cui,

Jian Wang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 4502 - 4507

Published: Jan. 1, 2024

A photoinduced formal deformylative phosphonylation utilizing easily available aldehydes was established, providing a practical synthetic route to alkylphosphonates from aliphatic aldehydes.

Language: Английский

Citations

4
Recent developments in the synthesis of pharmacological alkyl phosphonates DOI Creative Commons

C. Nguyen Xuan,

Zhimin Zhu,

Ziyang Li

et al.

Advanced Agrochem, Journal Year: 2024, Volume and Issue: 4(1), P. 13 - 29

Published: July 27, 2024

Organophosphate analogues are commonly occurring structural features that widely present in numerous natural substances, biologically active molecules and modern pharmaceutical compounds. The development of efficient strategies for the preparation these is still attractive but challenging organophosphorus chemistry. In order to fill this gap, different new routes have been discovered including direct phosphonylation alkyl radicals, indirect Arbuzov radicals nucleopilic phosphorus. short review, we attempted summarize recent developments synthesis phosphonates facilitate green pharmacological by emphasizing their variety products, specificity relevance, providing underlying mechanistic rationale whenever it possible. We aim provide readers with a comprehensive understanding current state field contribute future research.

Language: Английский

Citations

3