[Co(TPP)]–Catalyzed Carbene Transfer from Acceptor–Acceptor Iodonium Ylides via N-enolate Carbene Radicals DOI Creative Commons
Roel Epping,

Mees M. Hoeksma,

Eduard O. Bobylev

et al.

Published: June 15, 2021

<b>Abstract: </b>Square-planar cobalt(II)-systems have emerged as powerful carbene transfer catalysts for the synthesis of a variety (hetero)cyclic compounds via redox non-innocent Co(III)-carbene radical intermediates. Spectroscopic detection and characterization these reactive intermediates has thus far been limited to few scattered experiments, in part due fact that most studies focused on mono-substituted precursors. In this work, we demonstrate unique formation disubstituted cobalt(III)-carbene radicals reactions between cobalt(II)-porphyrin com-plex with acceptor-acceptor iodaneylidenes (iodonium ylides) We report detailed spectroscopic resulting species, their application styrene cyclopropanation. particular, iodonium ylides generate novel bis-carbenoid species leading reversible substrate-promoted ligand modification commercially available [Co(TPP)]-catalyst. Two interconnected catalytic cycles are involved overall reaction mono-terminal an unprecedented N-enolate-carbene intermediate respective key mono- bis-carbene cycles. Notably, N-enolate is not catalyst deactivation pathway, both moieties can be transferred units styrene. The provide picture new [Co(TPP)]-catalyzed from ylides. findings supported by unequivocal & products (EPR, UV-Vis, HR-MS, NMR, in-situ ATR-FT-IR, SC-XRD), Hammett analysis, mechanistic control DFT pathway profiling NEVPT2-CASSCF electronic structure calculations.<br>

Language: Английский

Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents DOI Creative Commons
Akira Yoshimura, Viktor V. Zhdankin

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

Citations

28
Hypervalent iodine reactions utilized in carbon–carbon bond formations DOI
I. F. Dempsey Hyatt,

Loma Dave,

Navindra David

et al.

Organic & Biomolecular Chemistry, Journal Year: 2019, Volume and Issue: 17(34), P. 7822 - 7848

Published: Jan. 1, 2019

This review covers recent developments of hypervalent iodine chemistry in dearomatizations, radicals, iodine-guided electrophilic substitution, arylations, photoredox, and more.

Language: Английский

Citations

115
Recent progress in the application of iodonium ylides in organic synthesis DOI
Xia Mi, Chao Pi, Weisheng Feng

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(24), P. 6999 - 7015

Published: Jan. 1, 2022

This review summarizes the recent advances in synthetic application of iodonium ylides covering 2017 to 2022.

Language: Английский

Citations

39
Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes DOI
Tristan Chidley, Islam Jameel,

Shafa Rizwan

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(47), P. 16959 - 16965

Published: Sept. 5, 2019

A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures alkenes β-dicarbonyl-derived iodonium ylides are irradiated with light from blue LEDs. This metal-free gives in yields up to 96 %, operative cyclic acyclic ylides, proceeds a variety electronically-diverse alkenes. Computational analysis explains the high selectivity observed, which derives exclusive HOMO LUMO excitation, instead free carbene generation. The procedure operationally simple, uses no photocatalyst, provides access one step important building blocks for complex molecule synthesis.

Language: Английский

Citations

42
Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions DOI
Neha Rani, Rinku Soni, Monika Sihag

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(11), P. 1798 - 1848

Published: April 21, 2022

Abstract This review outlines the progress over recent years in reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium cobalt. enables organic transformations complimentary to traditional manifolds. Hypervalent play a preeminent role chemistry due their versatile reactivity, heteroatom ligands mild reaction conditions. These combination metal compounds are used many synthetically useful oxidation, rearrangement, amination, halogenation, amidation, ring‐opening, cyclization C−H C−C functionalization reactions, etc . which discussed here. magnified image

Language: Английский

Citations

21
Rhodium-catalyzed C–H activation/cyclization of aryl sulfoximines with iodonium ylides towards polycyclic 1,2-benzothiazines DOI
Gao Huang,

Yujia Shan,

Jin‐Tao Yu

et al.

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(46), P. 10085 - 10089

Published: Jan. 1, 2021

The synthesis of 1,2-benzothiazine derivatives through rhodium-catalyzed C-H activation/cyclization S-aryl sulfoximines with iodonium ylides was developed for the first time. In this report, and N-H bond functionalization realized towards a series tricyclic tetracyclic sulfoximine moderate to excellent yields under simple reaction conditions.

Language: Английский

Citations

18
Copper-Catalyzed/Hypervalent Iodine-Mediated Functionalization of Unactivated Compounds DOI Open Access
Marta Papis, Francesca Foschi, Sara Colombo

et al.

Catalysts, Journal Year: 2023, Volume and Issue: 13(9), P. 1243 - 1243

Published: Aug. 26, 2023

The functionalization of unactivated substrates through the combination copper catalysts and hypervalent iodine reagents represents a versatile tool in organic synthesis to access various classes compounds. derivatives can be used simply as oxidizing agents regenerate catalytic species or they associate starting material. In this review, special attention will paid methodologies which provide introduction nucleophiles into reagent by use suitable benziodoxol(on)es iodonium salts. Many reactions concern C- N-arylations, but may also involve formation different carbon–carbon carbon–nitrogen bonds, carbon–oxygen well carbon–halogen carbon–phosphorus bonds.

Language: Английский

Citations

6
Direct Synthesis of Indolines via Cyclization of Tertiary Aryl Amines with Iodonium Ylides under Sole Visible Light Irradiation DOI

Yan‐Rui Zhao,

Lei Li, Jun Xuan

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 365(1), P. 110 - 115

Published: Dec. 2, 2022

Abstract Herein we reported a direct synthesis series of indolines through cyclization tertiary aryl amines with iodonium ylides. This reaction occurred under sole visible‐light irradiation at room temperature without the addition any photocatalysts and additives. Preliminary mechanism studies revealed that an electron donor‐acceptor (EDA) complex between ylides should be formed during reaction. magnified image

Language: Английский

Citations

9
The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2018 DOI

James W. Herndon

Coordination Chemistry Reviews, Journal Year: 2019, Volume and Issue: 401, P. 213051 - 213051

Published: Sept. 25, 2019

Language: Английский

Citations

11
Blue LED Irradiation of Iodonium Ylides Gives Diradical Intermediates for Efficient Metal‐free Cyclopropanation with Alkenes DOI
Tristan Chidley, Islam Jameel,

Shafa Rizwan

et al.

Angewandte Chemie, Journal Year: 2019, Volume and Issue: 131(47), P. 17115 - 17121

Published: Sept. 5, 2019

Abstract A facile and highly chemoselective synthesis of doubly activated cyclopropanes is reported where mixtures alkenes β‐dicarbonyl‐derived iodonium ylides are irradiated with light from blue LEDs. This metal‐free gives in yields up to 96 %, operative cyclic acyclic ylides, proceeds a variety electronically‐diverse alkenes. Computational analysis explains the high selectivity observed, which derives exclusive HOMO LUMO excitation, instead free carbene generation. The procedure operationally simple, uses no photocatalyst, provides access one step important building blocks for complex molecule synthesis.

Language: Английский

Citations

10