LiHMDS-Promoted Palladium or Iron-Catalyzed <i>ipso</i>-Defluoroborylation of Aryl Fluorides

Zhao, Xuhui; Wu, Mingsheng; Liu, Yisen; Cao, Song

doi:10.1021/acs.orglett.8b02228

Cited by 34 publications

(25 citation statements)

References 57 publications

(30 reference statements)

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“…Cao et al reported an iron-catalyzed defluoroborylation of aryl fluorides promoted by LiHMDS in the mixture solvents (Scheme 14). [54] This method could synthesize aryl boronate esters through the cross-coupling reaction of aryl fluorides with B 2 pin 2 without the use of ligands. However, only biaryl fluorides were suitable for this system, and the desired products were obtained in moderate yields.…”

Section: Iron-catalyzed Csp 2 à B Bond Formationmentioning

confidence: 99%

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

et al. 2020

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Carbon-heteroatom bonds are ubiquitous among pesticides, pharmaceutical agents, and natural products. In recent years, significant progress has been made in transition-metal-catalyzed carbon-heteroatom bond formation. Especially, iron-catalyzed reactions have become a focused area in organic chemistry owing to their advantages of low cost, economical and environmental benignity. This review intends to summarize the recent advances in the construction of carbon-heteroatom bonds via cross-coupling reactions using iron as a catalyst, including the formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds. A series of nucleophilic heteroatoms reagents, reaction classifications, and iron catalytic systems are discussed. In addition, some mechanistic studies have also been described. formation of CÀ N, CÀ O, CÀ S, CÀ B, and CÀ Si bonds are mainly focused. 2. Iron-Catalyzed CÀ N Bond Formation The construction of CÀ N bond by transition metal-catalyzed is one of the most significant transformations in organic synthesis, which is widely employed in chemical, pharmaceutical, and materials industries. [8] The classical method to access CÀ N bond is through the transition metal-catalyzed cross-coupling reaction between aryl or alkenyl halides and amines, also known as Buchwald-Hartwig amination reaction. In recent years, the formation of CÀ N bond via CÀ H activation has been welldocumented. [9] After decades of development, the great progress has been achieved in the transition metals (Cu, Pd, Ni, Fe, Co) catalyzed the construction of the CÀ N bond. [10] However, compared with other transition metals, iron-catalyzed CÀ N bond formation has less been studied, which might be caused by the negative effect of trace metals. [21-22] 2.1. Iron-Catalyzed CspÀ N Bond Formation Alkynamines are essential compounds, widely used in organic reactions such as pericyclic reaction, tandem RCM, Pauson-Khand reaction, Kinugasa reaction, Saucy-Marbet rearrangement, and Ficini-Claisen rearrangement. [11] In 2009, Zhang and coworkers [11e] developed the first example of iron-catalyzed amination of alkynyl bromides (Scheme 1). Nucleophiles such as amide, sulfonamide, and indole could react with alkynyl bromides to obtain alkynamines in high yields under FeCl 3 * 6H 2 O and DMEDA catalytic system. This reaction exhibits good functional group tolerance, and the functional groups

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Section: Iron-catalyzed Csp 2 à B Bond Formationmentioning

confidence: 99%

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

et al. 2020

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“…The reaction mechanism of the coupling reactions with 1-fluoro-2,2-diiodovinylarenes is not clear at this time. 14 We found that C−F bond of fluoroalkenes 6b and 7b can be activated by palladium to react with bis(pinacolato)diboron (B 2 Pin 2 ) to furnish the corresponding vinylboranes with good yields (Scheme 6). 15 In summary, we have developed a simple and efficient method for the synthesis of 1-fluoro-2,2-diiodovinylarenes via the decarboxylation of alkynoic acids.…”

Section: Scheme 3 Control Experimentsmentioning

confidence: 99%

Silver-Mediated Decarboxylative Fluorodiiodination of Alkynoic Acids: Synthesis of Regio- and Stereoselective Fluoroalkenes

Jayaraman

Lee

2019

Org. Lett.

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A variety of arylalkynoic acids reacted with 1,3diiodo-5,5-dimethylhydantoin and HF•pyridine in the presence of AgOAc to provide the corresponding 1-fluoro-2,2-diiodovinylarenes in good yields and high regioselectivity. In addition, Pd-catalyzed cross-coupling reaction of 1-fluoro-2,2-diiodovinylarenes afforded diaryl coupling products in the Suzuki reaction and monoaryl coupling products with high stereoselectivity in the Hiyama reaction. It was found that C−Factivated borylation of fluoroalkenes using Pd catalyst afforded the vinylboranes with good yields.

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“…从 XPS 的元素分析结果可以看出(表 S1), 相比于 H-CMP, F-CMP 在含有碳和氧的同时, 氟元素的含量也达到 11.74 wt%, 证实了聚合物中氟元素的成功引入. F-CMP 中氟含量比理论值低, 可能是因为在过渡金属钯的催化下, 聚合过程中部分缺陷处的碳氟键断裂, 氟元素以氟负离子的形式离去 [34] . [35] .…”

Section: 结果与讨论unclassified

Preparation and Adsorption Application Study of Fluorine-containing Conjugated Microporous Polymers

Yue¹,

Qian²,

Kong³

et al. 2019

Acta Chim. Sinica

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Water pollution arising from ever-growing domestic sewage and industrial organic pollutants has caused severe environmental and ecological problems in many parts of the world. It is urgent to seek appropriate ways to resolve oily wastewater and organic solvent pollution. Currently, physical adsorption is considered to be one of the most important methods to eliminate the oil contaminations in water thanks to its high efficiency and low cost. However, traditional adsorbent materials, such as activated carbon, zeolite and natural fibers, often suffer from low adsorption capacities, poor adsorption selectivity and recyclability. Thus, it is still of great importance to develop new absorbent materials for the separation and removal of oils or organic pollutants from water to address environmental issues. Conjugated microporous polymers (CMPs) are a class of organic porous polymers that have attracted extensive attention thanks to their large specific surface area, good physicochemical stability and unique extended π-conjugation along the polymer skeleton. Here we report a fluorine-containing conjugated microporous polymer (F-CMP), which was synthesized via Sonogashira cross-coupling reaction from 1,3,5-trifluoro-2,4,6-triiodobenzene and 1,3,5-triethynylbenzene. As a comparison, fluorine-free conjugated microporous polymer (H-CMP) was synthesized in the same condition from 1,3,5-tribromobenzene and 1,3,5-triethynybenzene. By introducing fluorine atom into the conjugated microporous skeleton, the contact angle of F-CMP with water reaches 145°, exhibiting excellent hydrophobicity. Nitrogen adsorption/desorption isotherms of the F-CMP show a high specific surface area of 638 m 2 •g-1 , and the pore size distribution analysis shows the existence of both micropores and macropores. It can be obtained by adsorption experiments of oil and organic solvents that the adsorption capability of F-CMP increases significantly compared with its fluorine-free counterpart with similar structural skeleton. Due to high hydrophobicity and porous properties, F-CMP shows excellent adsorption properties towards to the removal of organic solvents and oils. The adsorption capability of F-CMP towards pump oil and chloroform can reach 40 g/g and 43 g/g, respectively. Meanwhile, F-CMP shows rapid adsorption rate and excellent adsorption recyclability. Thus, F-CMP displays promising application prospects in the field of organic pollutant adsorption and environmental remediation.

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LiHMDS-Promoted Palladium or Iron-Catalyzed ipso-Defluoroborylation of Aryl Fluorides

Cited by 34 publications

References 57 publications

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds

Silver-Mediated Decarboxylative Fluorodiiodination of Alkynoic Acids: Synthesis of Regio- and Stereoselective Fluoroalkenes

Preparation and Adsorption Application Study of Fluorine-containing Conjugated Microporous Polymers

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