Organoselenium Compounds: Chemistry and Applications in Organic Synthesis DOI Open Access

Juan M. Sonego,

Sheila I. de Diego,

Sergio H. Szajnman

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(52)

Published: June 28, 2023

Abstract Selenium, originally described as a toxin, turns out to be crucial trace element for life that appears selenocysteine and its dimer, selenocystine. From the point of view drug developments, selenium‐containing drugs are isosteres sulfur oxygen with advantage presence selenium atom confers antioxidant properties high lipophilicity, which would increase cell membrane permeation leading better oral bioavailability. In this article, we have focused on relevant features atom, above all, corresponding synthetic approaches access variety organoselenium molecules along proposed reaction mechanisms. The preparation biological selenosugars, including selenoglycosides, selenonucleosides, selenopeptides, other compounds will treated. We attempted condense most important aspects interesting examples chemistry into single article.

Language: Английский

Inverse electron demand Diels–Alder reactions in chemical biology DOI Creative Commons
Bruno L. Oliveira, Zijian Guo, Gonçalo J. L. Bernardes

et al.

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(16), P. 4895 - 4950

Published: Jan. 1, 2017

The emerging inverse electron demand Diels–Alder (IEDDA) reaction stands out from other bioorthogonal reactions by virtue of its unmatchable kinetics, excellent orthogonality and biocompatibility.

Language: Английский

Citations

898
Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts DOI Creative Commons
Daniel Kaiser, Immo Klose,

Rik Oost

et al.

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(14), P. 8701 - 8780

Published: June 25, 2019

Organosulfur compounds have long played a vital role in organic chemistry and the development of novel chemical structures architectures. Prominent among these organosulfur are those involving sulfur(IV) center, which been subject countless investigations over more than hundred years. In addition to list textbook sulfur-based reactions, there has sustained interest organosulfur(IV) recent Of particular within is ease with synthetic chemist can effect wide range transformations through either bond formation or cleavage at sulfur. This review aims cover developments past decade molecules provide insight into both reactions critically rely on this versatile element diverse scaffolds that thereby be synthesized.

Language: Английский

Citations

698
The unique fluorine effects in organic reactions: recent facts and insights into fluoroalkylations DOI Creative Commons
Chuanfa Ni, Jinbo Hu

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(20), P. 5441 - 5454

Published: Jan. 1, 2016

Fluoroalkylation reaction, featuring the transfer of a fluoroalkyl group to substrate, is straightforward and efficient method for synthesis organofluorine compounds. In fluoroalkylation reactions, fluorine substitution can dramatically influence chemical outcome. On one hand, chemistry alkylation with non-fluorinated reagents may not be applicable fluoroalkylations, so it necessary tackle effects achieve reactions. other bring about new reactivities transformations that cannot realized in reagents; thus, used explore synthetic methods. This tutorial review provides brief overview unique recently developed nucleophilic, electrophilic, radical, transition metal-mediated reactions by comparing either their counterparts or fluorinated different numbers substituents.

Language: Английский

Citations

600
Modern Transition-Metal-Catalyzed Carbon–Halogen Bond Formation DOI

David A. Petrone,

Juntao Ye, Mark Lautens

et al.

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(14), P. 8003 - 8104

Published: June 24, 2016

The high utility of halogenated organic compounds has prompted the development a vast number transformations which install carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and use stoichiometric and/or toxic reagents. In this regard, using transition metals catalyze synthesis organohalides become mature field in itself, applying technologies allowed for decrease production waste, higher levels regio- stereoselectivity, ability produce enantioenriched target compounds. Furthermore, offer distinct advantage possessing diverse spectrum mechanistic possibilities translate capability apply new substrate classes afford novel difficult-to-access structures. This Review provides comprehensive coverage modern metal-catalyzed syntheses via array mechanisms. Attention is given seminal organometallic studies led corresponding catalytic processes being realized. By breaking down into aryl, vinyl, alkyl halides, it becomes clear methods surfaced as most favored each individual class. general, pronounced shift toward C-H bonds key functional groups, addition proceed by catalytic, radical-based mechanisms occurred. Although always evolving, appears be heading direction starting materials with significantly lower degree prefunctionalization less expensive abundant metal catalysts.

Language: Английский

Citations

577
Toolbox for Distal C–H Bond Functionalizations in Organic Molecules DOI

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

Citations

380
Fluorination methods in drug discovery DOI
Damian E. Yerien, Sergio M. Bonesi, Al Postigo

et al.

Organic & Biomolecular Chemistry, Journal Year: 2016, Volume and Issue: 14(36), P. 8398 - 8427

Published: Jan. 1, 2016

Late stage fluorination methods applied to biologically-active drugs have provided the pharmaceutical industry with new leads that show improved properties such as modulation of lipophilicity, electronegativity, basicity, bioavailability, and deceleration metabolic degradation.

Language: Английский

Citations

314
Beyond ferryl-mediated hydroxylation: 40 years of the rebound mechanism and C–H activation DOI Creative Commons
Xiongyi Huang, John T. Groves

JBIC Journal of Biological Inorganic Chemistry, Journal Year: 2016, Volume and Issue: 22(2-3), P. 185 - 207

Published: Dec. 1, 2016

Since our initial report in 1976, the oxygen rebound mechanism has become consensus mechanistic feature for an expanding variety of enzymatic C–H functionalization reactions and small molecule biomimetic catalysts. For both biotransformations models, hydrogen atom abstraction from substrate (R–H) by high-valent iron-oxo species (Fen=O) generates a radical reduced iron hydroxide, [Fen−1–OH ·R]. This caged pair then evolves on complicated energy landscape through number reaction pathways, such as to form R–OH, non-oxygen affording R–X, electron transfer incipient yield carbocation, R+, desaturation olefins, cage escape. These various flavors process, often competition with each other, give rise wide range performed iron-containing oxygenases. In this review, we first recount history mechanisms, their general features, key intermediates involved. We will discuss detail factors that affect behavior lifetimes radicals. Several representative examples transformations are selected illustrate how behaviors ·R] determine eventual outcome. Finally, powerful potential "radical rebound" processes paradigm developing novel synthetic, envision new chemistry continue arise bridging synthetic organic chemistry.

Language: Английский

Citations

297
Selectivity of C–H Activation and Competition between C–H and C–F Bond Activation at Fluorocarbons DOI
Odile Eisenstein,

Jessica Milani,

Robin N. Perutz

et al.

Chemical Reviews, Journal Year: 2017, Volume and Issue: 117(13), P. 8710 - 8753

Published: June 27, 2017

Partially fluorinated alkanes, arenes, and alkenes can be transformed by a variety of transition metal lanthanide systems. Although the C-H bond is weaker than C-F regardless hybridization carbon, reaction at usually more exothermic corresponding bonds. Both bonds are activated systems, but preference for activating these depends on nature hydrocarbon system, so that directed exclusively toward or yield mixture products. Additionally, presence fluorine differentiates between different positions resulting in regioselective activation; paradoxically, strongest reacts preferentially. The purpose this review to describe field reactions partially substrates with atoms, ions, molecular complexes. controlling physical properties (thermodynamics kinetics) described first, followed description stoichiometric reactions, competition activations as focus. A few representative catalytic systems discussed. also highlights benefit combining experimental theoretical studies.

Language: Английский

Citations

290
Chemistry for Positron Emission Tomography: Recent Advances in 11C‐, 18F‐, 13N‐, and 15O‐Labeling Reactions DOI
Xiaoyun Deng, Jian Rong, Lu Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(9), P. 2580 - 2605

Published: July 28, 2018

Positron emission tomography (PET) is a molecular imaging technology that provides quantitative information about function and metabolism in biological processes vivo for disease diagnosis therapy assessment. The broad application rapid advances of PET has led to an increased demand new radiochemical methods synthesize highly specific molecules bearing positron-emitting radionuclides. This Review overview commonly used labeling reactions through examples clinically relevant tracers highlights the most recent developments breakthroughs over past decade, with focus on

Language: Английский

Citations

283
New Horizons of Photocatalytic Fluoromethylative Difunctionalization of Alkenes DOI Creative Commons
Takashi Koike, Munetaka Akita

Chem, Journal Year: 2017, Volume and Issue: 4(3), P. 409 - 437

Published: Dec. 21, 2017

Language: Английский

Citations

257