Synthetic Methods Driven by the Photoactivity of Electron Donor–Acceptor Complexes

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(12), P. 5461 - 5476

Published: March 5, 2020

The association of an electron-rich substrate with electron-accepting molecule can generate a new molecular aggregate in the ground state, called electron donor-acceptor (EDA) complex. Even when two precursors do not absorb visible light, resulting EDA complex often does. In 1952, Mulliken proposed quantum-mechanical theory to rationalize formation such colored complexes. However, and besides few pioneering studies 20th century, it is only past years that photochemistry has been recognized as powerful strategy for expanding potential visible-light-driven radical synthetic chemistry. Here, we explain why this photochemical approach was overlooked so long. We critically discuss historical context, scientific reasons, serendipitous observations, landmark discoveries were essential progress field. also outline future directions identify key advances are needed fully exploit photochemistry.

Language: Английский

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Technological Innovations in Photochemistry for Organic Synthesis: Flow Chemistry, High-Throughput Experimentation, Scale-up, and Photoelectrochemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2752 - 2906

Published: Aug. 10, 2021

Photoinduced chemical transformations have received in recent years a tremendous amount of attention, providing plethora opportunities to synthetic organic chemists. However, performing photochemical transformation can be quite challenge because various issues related the delivery photons. These challenges barred widespread adoption steps industry. past decade, several technological innovations led more reproducible, selective, and scalable photoinduced reactions. Herein, we provide comprehensive overview these exciting advances, including flow chemistry, high-throughput experimentation, reactor design scale-up, combination photo- electro-chemistry.

Language: Английский

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Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(2), P. 766 - 897

Published: Dec. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Language: Английский

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Photocatalysis in the Life Science Industry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 2907 - 2980

Published: Sept. 24, 2021

In the pursuit of new pharmaceuticals and agrochemicals, chemists in life science industry require access to mild robust synthetic methodologies systematically modify chemical structures, explore novel space, enable efficient synthesis. this context, photocatalysis has emerged as a powerful technology for synthesis complex often highly functionalized molecules. This Review aims summarize published contributions field from industry, including research industrial-academic partnerships. An overview developed strategic applications synthesis, peptide functionalization, isotope labeling, both DNA-encoded traditional library is provided, along with summary state-of-the-art photoreactor effective upscaling photocatalytic reactions.

Language: Английский

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Manganese‐Catalyzed C−H Alkynylation: Expedient Peptide Synthesis and Modification

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(12), P. 3172 - 3176

Published: Feb. 9, 2017

Abstract Manganese(I)‐catalyzed C−H alkynylations with organic halides occurred unparalleled substrate scope, and thus enabled step‐economical functionalizations silyl, aryl, alkenyl, alkyl haloalkynes. The versatility of the manganese(I) catalysis manifold couplings haloalkynes featuring, among others, fluorescent labels, steroids, amino acids, thereby setting stage for peptide ligation as well efficient molecular assembly acyclic cyclic peptides. A plausible catalytic cycle was proposed.

Language: Английский

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Photocatalytic Modification of Amino Acids, Peptides, and Proteins

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 25(1), P. 26 - 42

Published: July 31, 2018

Abstract In the last decade, visible‐light photoredox catalysis has emerged as a powerful strategy to enable novel transformations in organic synthesis. Owing mild reaction conditions (i.e., room temperature, use of visible light) and high functional‐group tolerance, could represent an ideal for chemoselective biomolecule modification. Indeed, recent trend is its application development methodologies amino acid Herein, up‐to‐date overview photocatalytic modification single acids, peptides, proteins provided. The advantages offered by suitability biocompatible are described. addition, brief consideration current limitations approaches, well future challenges be addressed, discussed.

Language: Английский

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Application of metal oxide semiconductors in light-driven organic transformations

Catalysis Science & Technology, Journal Year: 2019, Volume and Issue: 9(19), P. 5186 - 5232

Published: Jan. 1, 2019

Herein, we provide an up-to-date overview of metal oxide semiconductors (MOS) as versatile and inexpensive photocatalysts to enable light-driven organic transformations.

Language: Английский

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Histidine-Specific Peptide Modification via Visible-Light-Promoted C–H Alkylation

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(45), P. 18230 - 18237

Published: Oct. 21, 2019

Histidine (His) carries a unique heteroaromatic imidazole side chain and plays irreplaceable functional roles in peptides proteins. Existing strategies for site-selective histidine modification predominantly rely on the N-substitution reactions of moderately nucleophilic group, which inherently suffers from interferences lysine cysteine residues. Chemoselective remains one most difficult challenges peptide chemistry. Herein, we report via radical-mediated chemoselective C–H alkylation using C4-alkyl-1,4-dihydropyridine (DHP) reagents under visible-light-promoted conditions. The method exploits electrophilic reactivity ring Minisci-type reaction pathway. This exhibits an exceptionally broad scope both DHP reagents. Its utility has been demonstrated series important drugs, complex natural products, small protein. Distinct reactions, unsubstituted nitrogen groups modified are conserved alkylated products.

Language: Английский

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Visible-Light-Mediated Modification and Manipulation of Biomacromolecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(2), P. 1752 - 1829

Published: Sept. 21, 2021

Chemically modified biomacromolecules─i.e., proteins, nucleic acids, glycans, and lipids─have become crucial tools in chemical biology. They are extensively used not only to elucidate cellular processes but also industrial applications, particularly the context of biopharmaceuticals. In order enable maximum scope for optimization, it is pivotal have a diverse array biomacromolecule modification methods at one's disposal. Chemistry has driven many significant advances this area, especially recently, numerous novel visible-light-induced photochemical approaches emerged. these reactions, light serves as an external source energy, enabling access highly reactive intermediates under exceedingly mild conditions with exquisite spatiotemporal control. While UV-induced transformations on biomacromolecules date back decades, visible unmistakable advantage being considerably more biocompatible, spectrum visible-light-driven now available, chiefly proteins acids. This review will discuss modifications native functional groups (FGs), including functionalization, labeling, cross-linking techniques well utility oxidative degradation mediated by photochemically generated oxygen species. Furthermore, non-native, bioorthogonal FGs be addressed, photoclick chemistry DNA-encoded library synthesis that allow manipulation activity biomacromolecule.

Language: Английский

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Site-selective tyrosine bioconjugation via photoredox catalysis for native-to-bioorthogonal protein transformation

Nature Chemistry, Journal Year: 2021, Volume and Issue: 13(9), P. 902 - 908

Published: June 28, 2021

Language: Английский

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