Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents

Chemical Reviews, Год журнала: 2024, Номер unknown

Опубликована: Сен. 13, 2024

Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. iodine are commonly used synthetically important halogenations, oxidations, aminations, heterocyclizations, various oxidative functionalizations of substrates. Iodonium salts arylating reagents, while iodonium ylides imides excellent carbene nitrene precursors. Various derivatives benziodoxoles, such azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, alkenylbenziodoxoles group transfer the presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Development hypervalent catalytic systems discovery highly enantioselective reactions chiral represent a particularly recent achievement field chemistry. Chemical transformations promoted by many cases unique cannot be performed any other common, non-iodine-based reagent. This review covers literature published mainly last 7-8 years, between 2016 2024.

Язык: Английский

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Copper-Catalyzed Enantioselective [4π + 2σ] Cycloaddition of Bicyclobutanes with Nitrones

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 25, 2024

The selective construction of bridged bicyclic scaffolds has garnered increasing attention because their extensive use as saturated bioisosteres arene in pharmaceutical industry. However, sharp contrast to racemic counterparts, assembling chiral structures an enantioselective and regioselective manner remains challenging. Herein, we describe our protocol for constructing 2-oxa-3-azabicyclo[3.1.1]heptanes (BCHeps) by [4π + 2σ] cycloadditions bicyclo[1.1.0]butanes (BCBs) nitrones taking advantage a copper(II) complex Lewis acid catalyst. This method features mild conditions, good functional group tolerance, high yield (up 99%), excellent enantioselectivity 99% ee). Density theory (DFT) calculation elucidates the origin reaction's mechanism BCB activation Cu(II) complex.

Язык: Английский

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Recent Advances in Visible Light‐Mediated Radical Fluoro‐alkylation, ‐alkoxylation, ‐alkylthiolation, ‐alkylselenolation, and ‐alkylamination

The Chemical Record, Год журнала: 2023, Номер 23(9)

Опубликована: Май 22, 2023

Abstract In the last few years, many reagents and protocols have been developed to allow for efficient fluorofunctionalization of a diverse set scaffolds ranging from alkanes, alkenes, alkynes, (hetero)arenes. The concomitant rise organofluorine chemistry visible light‐mediated synthesis synergistically expanded fields mutually benefitted developments in both fields. this context, light driven formations radicals containing fluorine major focus discovery new bioactive compounds. This review details recent advances progress made fluoroalkylation heteroatom centered radical generation.

Язык: Английский

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N-Halosuccinimide enables cascade oxidative trifluorination and halogenative cyclization of tryptamine-derived isocyanides

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Окт. 16, 2024

Both the pyrroloindoline core and N-CF

Язык: Английский

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Photoredox/Copper Dual-Catalyzed Three-Component Perfluoroalkyl Trifluoromethylthiolation of Alkenes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Фев. 20, 2025

A new three-component 1,2-perfluoroalkyl trifluoromethylthiolation of alkenes via dual photoredox/copper catalysis has been established, affording a variety CnF2n+1/CF3S-containing molecules under mild conditions in redox-neutral manner. This protocol exhibits excellent functional group tolerance, broad compatibility with various and perfluoroalkyl iodides, potential utility the modification bioactive molecules.

Язык: Английский

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α-Selective syn-Carbotrifluoromethylthiolation of Alkynes

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Март 3, 2025

Trifluoromethylthiolative difunctionalization of alkynes typically proceeds in an anti-fashion delivering the SCF3 group β-position (anti-Markovnikov). Herein, we disclose a vicinal syn-arylation-trifluoromethylthiolation enabling α-selective introduction (Markovnikov). The unique selectivity was achieved via merge Ni-catalyzed carbomagnesiation with subsequent Cu-mediated trifluoromethylthiolation resulting vinyl-magnesium species. former component sequential process determines both regio- and stereoselectivity overall transformation.

Язык: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Апрель 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Язык: Английский

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Lewis Acid Promoted Vicinal Oxytrifluoromethylselenolation of Alkenes

Organic Letters, Год журнала: 2023, Номер 25(18), С. 3210 - 3215

Опубликована: Апрель 28, 2023

Herein, we have developed a metal-free, Lewis acid promoted vicinal oxytrifluoromethylselenolation of alkenes using trifluoromethyl selenoxides as electrophilic trifluoromethylselenolation reagents and alcohols nucleophiles. With less steric good nucleophilic solvents (such ethanol methol), Tf2O-catalyzed could be realized, while stoichiometric Tf2O was required to promote full transformation with isopropanol tert-butanol). The reaction featured substrate scope, functional group compatibility, diastereoselectivity. This method further applied oxytrifluoromethylselenolation, aminotrifluoromethylselenolation nucleophiles under modified conditions. A mechanism involving seleniranium ion proposed based on the preliminary results.

Язык: Английский

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Transition-Metal-Free C–H Trifluoromethylthiolation of N,N-Disubstituted Enaminones To Access CF₃S-Functionalized Enaminones and Their Application in the Synthesis of CF₃S-Heteroaryls

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(12), С. 9078 - 9085

Опубликована: Июнь 3, 2024

The α-C–H trifluoromethylthiolation of N,N-disubstituted enaminones has been achieved with simple and cheap CF3SO2Na as the CF3S source. reactions were run at mild temperature (0 °C to rt) using POCl3 only reducing reagent. work represents first example on synthesis α-trifluoromethylthio via direct C–H functionalization. In addition, resulting CF3S-functionalized have proven useful building blocks in various heteroaromatic compounds by annulation reactions.

Язык: Английский

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Preparation and Reactivity Study of a Versatile Trifluoromethylthiolating Agent: S‐Trifluoromethyl Trifluoromethanesulfonothioate (TTST)

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(32)

Опубликована: Июнь 7, 2023

Abstract A novel, air and thermally stable, yet highly reactive trifluoromethylthiolating reagent, CF 3 SO 2 SCF ( 1 ), was prepared easily in one step from commercially inexpensive Na Tf O. is a versatile atom‐efficient reagent that can generate equivalent of S + , two equivalents − or combination S⋅/CF ⋅ species. Many high‐yielding reactions C O N ‐nucleophiles were achieved, including the simple‐step preparations many reported reagents. delivered hitherto hard‐to‐synthesize ArOSCF followed by novel II ‐rearrangement. Through Cu TDAE/Ph P combinations, generated anion species, photo‐catalyzed alkenes with provided /CF S‐containing products high atom‐efficiency.

Язык: Английский

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