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

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 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.

Language: Английский

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Condition-Controlled Selective Synthesis of Pyranone-Tethered Indazoles or Carbazoles through the Cascade Reactions of N-Nitrosoanilines with Iodonium Ylides

Organic Letters, Journal Year: 2023, Volume and Issue: 25(24), P. 4422 - 4428

Published: June 8, 2023

Presented herein is a condition-controlled selective synthesis of pyranone-tethered indazoles or carbazole derivatives via the cascade reactions N-nitrosoanilines with iodonium ylides. Mechanistically, formation former involves an unprecedented process including nitroso group-directed C(sp2)–H bond alkylation N-nitrosoaniline ylide followed by intramolecular C-nucleophilic addition to moiety, solvent-assisted cyclohexanedione ring opening, and transesterification/annulation. On contrary, latter initial annulation denitrosation. These developed protocols feature easily controllable selectivity, mild reaction conditions, clean sustainable oxidant (air), valuable products that are structurally diverse. In addition, utility was showcased their facile diverse transformations into synthetically biologically interesting compounds.

Language: Английский

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Catalytic and Base‐free Suzuki‐type α‐Arylation of Cyclic 1,3‐Dicarbonyls via a Cyclic Iodonium Ylide Strategy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(17)

Published: Feb. 22, 2024

Abstract To date, it remains challenging to achieve a general and catalytic α‐arylation of cyclic 1,3‐dicarbonyls, particularly ubiquitous heteroaromatic ones. In most cases, the preparation their medically significant arylated derivatives requires multistep synthetic sequences. Herein, we introduce new, convenient strategy involving conversion 1,3‐dicarbonyls iodonium ylides ( CIY s), followed by rhodium‐catalyzed with arylboronic reagents via carbene coupling. This approach is mild, operationally simple, base‐free, biocompatible, exhibits broad substrate scope (>100 examples), especially respect various ortho ‐substituted or base‐sensitive acids. Importantly, owing excellent compatibility acids boronate esters (ArBpin, ArBneop, ArBF 3 K), this method allows late‐stage installation heterocyclic 1,3‐dicarbonyl motifs in highly complex settings. The utility transformation further demonstrated through significantly simplifying synthesis several bioactive molecules natural products.

Language: Английский

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Rhodium-Catalyzed Difunctionalization of Alkenes Using Cyclic 1,3-Dicarbonyl-Derived Iodonium Ylides

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1886 - 1890

Published: Feb. 28, 2024

Herein, we introduce an iodonium ylide strategy to achieve novel α-alkylation of cyclic 1,3-dicarbonyls through harnessing C(sp3)–Rh species generated from 5-exo-trig cyclization provide rapid access molecular hybridization medically important isoindolin-1-ones and readily available substrates. This approach features mild conditions, good yield, excellent functional group tolerance, the simultaneous formation two new chemical bonds one stereogenic center. Moreover, hydroxyl resulting product provides a handle for downstream transformations. Importantly, also demonstrate this can be achieved in one-pot manner. A complex was prepared proved key intermediate.

Language: Английский

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Application of Sulfoxonium Ylides or Iodonium Ylides in Rhodium‐Catalyzed Synthesis of Phenanthrenes

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1744 - 1750

Published: Feb. 22, 2024

Abstract The transmetalation triggered rhodium‐catalyzed C−H bond activation and tandem annulation of 2‐biphenylboronic acids with sulfoxonium ylides or iodonium has been developed. Various products phenanthrenes were constructed under redox‐neutral conditions in 34–86% yields. Several mechanism exploration experiments derivatization reactions conducted sequence to gain a deeper understanding the process potential this transformation. It offers an alternative approach for synthesis phenanthrene derivatives.

Language: Английский

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A Carbene Relay Strategy for Cascade Insertion Reactions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 19, 2023

Abstract Insertion reactions that involve stabilized electrophilic metallocarbenes are of great importance for installing α‐heteroatoms to carbonyl compounds. Nevertheless, the limited availability carbene precursors restricts introduction only a single heteroatom. In this report, we describe new approach based on an I (III) /S (VI) reagent promotes cascade insertion heteroatoms. This is achieved by sequentially generating two α‐heteroatom‐substituted metal carbenes in one reaction. We found mixed ylide reacts efficiently with transition catalyst and X−H bond (where X=O, N). transformation leads sequential formation sulfoxonium‐ X‐substituted Rh‐carbenes, enabling further another Y−H bond. Remarkably, wide range symmetrical unsymmetrical α,α‐ O , ‐, N ‐subsituted ketones can be prepared under mild ambient conditions. addition, successfully demonstrated other cascades, such as CN/CN double amidation, C−H/C−S insertion, C−S/Y−H Y=S, N, O, C). Notably, latter cascades enabled simultaneous installation three functional groups α‐carbon compounds step. These demonstrate versatility our approach, allowing synthesis esters multiple using common precursor.

Language: Английский

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Carbene-induced ring-opening reactions of five-/six-membered cyclic ethers: expanding the frontiers of functional group introduction and molecular architecture construction

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The multi-component ring-opening reactions of cyclic ethers offer an efficient strategy for the rapid introduction multiple functional groups and construction complex molecular architectures.

Language: Английский

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Iodonium(III) Ylide: An Iodoalkylation Reagent with Aryne

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

A tandem Hexadehydro-Diels–Alder (HDDA)/[2 + 2] cycloaddition/aryl migration reaction of iodonium ylide with tetrayne is described, in which served as a unique double bond and reacted aryne to form four-membered iodonium(III) cycle, then converted iodoarene after aryl group from iodine adjacent carbon. This strategy allows the efficient construction fully substituted compounds.

Language: Английский

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Synthesis of 1-Aminoisoquinolines via Rh(III)-Catalyzed C–H Cascade Annulation of Benzamidines with Iodonium Ylides

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

A Rh(III)-catalyzed C-H cascade annulation reaction of benzamidine hydrochlorides with iodonium ylides has been successfully accomplished, providing an efficient strategy for the synthesis various 1-aminoisoquinoline derivatives in moderate to good yields. Here, ylide serves as accessible and safe carbene precursor. Further derivatizations were implemented demonstrate potential utility this reaction. Furthermore, photophysical properties these compounds may have applications photoelectric materials.

Language: Английский

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Substrate-Controlled Divergent Synthesis of Benzimidazole-Fused Quinolines and Spirocyclic Benzimidazole-Fused Isoindoles

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7513 - 7520

Published: May 9, 2024

A Rh(III)-catalyzed annulation of 2-arylbenzimidazoles with α-diazo carbonyl compounds via C–H activation/carbene insertion/intramolecular cyclization is explored. The switchable product selectivity achieved by the use distinct compounds. Benzimidazole-fused quinolines are obtained through [4 + 2] exclusively when 2-diazocyclohexane-1,3-diones used, where they act as a C2 synthon. Alternatively, diazonaphthalen-1(2H)-ones merely function one-carbon unit synthon to generate quaternary center 1] afford spirocyclic benzimidazole-fused isoindole naphthalen-2-ones. thorough mechanistic study reveals course reaction.

Language: Английский

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