Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases DOI

Tobias Betke,

Jun Higuchi,

Philipp Rommelmann

et al.

ChemBioChem, Journal Year: 2018, Volume and Issue: 19(8), P. 768 - 779

Published: Jan. 15, 2018

Abstract Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high‐volume, low‐price sectors, such as polymers, to low‐volume, high‐price chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation gas‐phase reaction at high temperature. Further popular approaches substitution or addition reactions with hydrogen cyanide derivatives thereof. drawback, however, very toxicity of cyanide. Recently, synthetic alternative, novel enzymatic approach towards nitriles has been developed aldoxime dehydratases, capable converting an one step through dehydration into nitriles. Because substrates easily accessible, this route interest purposes. However, whenever method organic synthesis, it raises question substrate scope key criteria application “synthetic platform technology”. Thus, review give overview current state synthesizing dehydratases. As recently emerging enzyme class, range already studied so far, comprising nonchiral aldoximes. This class dehydratases shows broad tolerance accepts aliphatic aromatic aldoximes, well arylaliphatic Furthermore, aldoximes stereogenic center also recognized enantioselectivities found 2‐arylpropylaldoximes, particular. It further noteworthy that enantiopreference depends on E Z isomers. opposite enantiomers accessible same racemic aldehyde enzyme.

Language: Английский

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications DOI
Mingzhu Lu, Jeffrey Goh, Manikantha Maraswami

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(24), P. 17479 - 17646

Published: Oct. 14, 2022

Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, advanced materials. Significant efforts have been made toward the development new practical methods to access this important class compounds by selectively activating alkenyl C(sp2)–H bonds recent years. In comprehensive review, we describe state-of-the-art strategies for direct functionalization sp2 C–H C–F until June 2022. Moreover, metal-free, photoredox, electrochemical also covered. For clarity, review has divided into two parts; first part focuses on currently available using different alkene as starting materials, second describes bond easily accessible gem-difluoroalkenes material. This includes scope, limitations, mechanistic studies, stereoselective control (using directing groups well metal-migration strategies), applications complex molecule synthesis where appropriate. Overall, aims document considerable advancements, current status, emerging work critically summarizing contributions researchers working fascinating area is expected stimulate novel, innovative, broadly applicable functionalizations coming

Language: Английский

Citations

150
Nickel-catalysed asymmetric hydrogenation of oximes DOI
Bowen Li, Jianzhong Chen, Dan Liu

et al.

Nature Chemistry, Journal Year: 2022, Volume and Issue: 14(8), P. 920 - 927

Published: June 13, 2022

Language: Английский

Citations

91
Nitrogen Effects Endowed by Doping Electron-Withdrawing Nitrogen Atoms into Polycyclic Aromatic Hydrocarbon Fluorescence Emitters DOI

Yimin Wu,

Xiaoyu Liu, Junjie Liu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15977 - 15985

Published: May 7, 2024

Unveiling innovative mechanisms to design new highly efficient fluorescent materials and, thereby, fabricate high-performance organic light-emitting diodes (OLEDs) is a concerted endeavor in both academic and industrial circles. Polycyclic aromatic hydrocarbons (PAHs) have been widely used as emitters blue OLEDs, but device performances are far from satisfactory. In response, we propose the concept of "nitrogen effects" endowed by doping electron-withdrawing nitrogen atoms into PAH fluorescence emitters. The presence n orbital on imine conducive promoting electron coupling, which leads increased molar absorptivity an accelerated radiative decay rate emitters, thereby facilitating Förster energy transfer (FET) process OLEDs. Additionally, electronically withdrawing enhances host–guest interactions, positively affecting FET horizontal orientation factor emitting layer. To validate concept, cobalt-catalyzed multiple C–H annulation has utilized incorporate alkynes imine-based frameworks, enables various imine-embedded (IE-PAH) cyclization demonstrates notable regioselectivity, offering practical tool precisely introduce peripheral groups at desired positions with bulky alkyl units positioned adjacent atoms, were previously beyond reach through Friedel–Crafts reaction. Blue OLEDs fabricated IE-PAHs exhibit outstanding performance maximum external quantum efficiency (EQEmax) 32.7%. This achievement sets groundbreaking record for conventional PAH-based EQEmax 24.0%.

Language: Английский

Citations

17
tert‐Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis DOI
Anjali Dahiya, Ashish Kumar Sahoo, Tipu Alam

et al.

Chemistry - An Asian Journal, Journal Year: 2019, Volume and Issue: 14(24), P. 4454 - 4492

Published: Sept. 20, 2019

The upsurge interest in the development of efficient methodologies for construction nitrogen-containing frameworks via use expedient reagents have been creating a renaissance contemporary organic chemistry. In this perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its unique structural features, it shows differential reactivity under different reaction conditions. These diverse reactivities resulted array complex N-containing molecules. primary objective present review bring latest findings TBN terms applications reactions (oxidation, diazotization, nitrosation, nitration, oximation, N-synthon, and miscellaneous reactions) into limelight. For simplicity brevity, each section are explained with mechanism formation selected examples given.

Language: Английский

Citations

95
Coating and Functionalization Strategies for Nanogels and Nanoparticles for Selective Drug Delivery DOI Creative Commons
Filippo Pinelli, Giuseppe Perale, Filippo Rossi

et al.

Gels, Journal Year: 2020, Volume and Issue: 6(1), P. 6 - 6

Published: Feb. 4, 2020

Drug delivery is a fascinating research field with several development opportunities. Great attention now focused on colloidal systems, nanoparticles, and nanogels the possibility of modifying them in order to obtain precise targeted drug systems. The aim this review give an overview main available surface functionalization coating strategies that can be adopted modify selectivity nanoparticles process final system great ability. We also highlight most important fields application these kinds systems we propose comparison between advantages disadvantages described strategies.

Language: Английский

Citations

89
1,4-Alkylcarbonylation of 1,3-Enynes to Access Tetra-Substituted Allenyl Ketones via an NHC-Catalyzed Radical Relay DOI
Lei Chen, Lin Chen, Simiao Zhang

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(21), P. 13363 - 13373

Published: Oct. 19, 2021

Reactions involving allenyl ion intermediates have been widely applied in the synthesis of functionalized allenes, but reactions radicals less studied and limited successful examples realized mainly by transition metal catalysis. We herein demonstrate generation N-heterocyclic carbene (NHC) organocatalysis their applications three-component radical relay 1,4-alkylcarbonylation 1,3-enynes without participation. This strategy could accommodate a collection different alkyl precursors such as CF3I, halides, cycloketone oxime esters, aliphatic carboxylic acid derived redox-active enabling convenient pathway to access range synthetically challenging tetra-substituted ketones with high regioselectivity. The key success this protocol relied on Csp-C(O)sp2 radical–radical coupling NHC-bound ketyl radicals, constructing ketone motifs highly efficient reaction pathway.

Language: Английский

Citations

86
Chalcone oxime derivatives as new inhibitors corrosion of carbon steel in 1 M HCl solution DOI
A. Thoume, D. Benmessaoud Left, Abdelhakim Elmakssoudi

et al.

Journal of Molecular Liquids, Journal Year: 2021, Volume and Issue: 337, P. 116398 - 116398

Published: May 5, 2021

Language: Английский

Citations

63
FDA-Approved Oximes and Their Significance in Medicinal Chemistry DOI Creative Commons

Jyothi Dhuguru,

Ievgen M. Zviagin, Rachid Skouta

et al.

Pharmaceuticals, Journal Year: 2022, Volume and Issue: 15(1), P. 66 - 66

Published: Jan. 4, 2022

Despite the scientific advancements, organophosphate (OP) poisoning continues to be a major threat humans, accounting for nearly one million cases every year leading at least 20,000 deaths worldwide. Oximes represent most important class in medicinal chemistry, renowned their widespread applications as OP antidotes, drugs and intermediates synthesis of several pharmacological derivatives. Common oxime based reactivators or nerve antidotes include pralidoxime, obidoxime, HI-6, trimedoxime methoxime, among which pralidoxime is only FDA-approved drug. Cephalosporins are β-lactam antibiotics serve widely acclaimed tools fighting bacterial infections. Oxime cephalosporins have emerged an with improved efficacy broad spectrum anti-microbial activity against Gram-positive Gram-negative pathogens. Among derivatives, cefuroxime, ceftizoxime, cefpodoxime cefmenoxime FDA approved oxime-based antibiotics. Given significance oximes, present paper, we put together all oximes discuss mechanism action, pharmacokinetics synthesis.

Language: Английский

Citations

56
Total Syntheses of Calyciphylline A-Type Alkaloids (−)-10-Deoxydaphnipaxianine A, (+)-Daphlongamine E and (+)-Calyciphylline R via Late-Stage Divinyl Carbinol Rearrangements DOI
Yan Zhang, Yuye Chen,

Manrong Song

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(35), P. 16042 - 16051

Published: Aug. 25, 2022

Among the famous Daphniphyllum alkaloids family, calyciphylline A-type subfamily has triggered particular interest from organic synthesis community in recent years. Here, we report divergent total syntheses of three alkaloids, namely, (−)-10-deoxydaphnipaxianine A, (+)-daphlongamine E, and (+)-calyciphylline R. Our work highlights an efficient, strategy via late-stage divinyl carbinol rearrangements, including unprecedented oxidative Nazarov electrocyclization using unfunctionalized tertiary unusual allylic alcohol rearrangement. A highly efficient "donor–acceptor" platinum catalyst was used for a critical nitrile hydration step. Moreover, power selective amide reductions also been showcased by novel classic tactics.

Language: Английский

Citations

39
Solvent-Controlled Silver Catalyzed Radical Transformation of α-Imino-Oxy Acids with Cyclic Aldimines DOI
Jingjing Wang, Yong Qin,

Ke Cui

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A silver-catalyzed cross coupling of cyclic aldimines and α-imino-oxy acids has been developed. The solvent-dependent reaction could selectively deliver either imine moiety retained nitriles or ring-opened oxonitriles in moderate yields.

Language: Английский

Citations

1