Copper‐Catalyzed Oxidative Cross‐Coupling of Electron‐Deficient Polyfluorophenylboronate Esters with Terminal Alkynes

Liu, Zhiqiang; Budiman, Yudha P.; Tian, Yaming; Friedrich, Alexandra; Huang, Mingming; Westcott, Stephen A.; Radius, Udo; Marder, Todd B.

doi:10.1002/chem.202002888

Cited by 16 publications

(14 citation statements)

References 121 publications

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“…The angle between Dipp 2 Im and the trans ‐ i Pr 2 Im ligand is 173.88(7)°. The molecule is further stabilized by π‐stacking [41f,h,51] between the C 6 F 5 ligand and one of the Dipp 2 Im phenyl substituents, as the angle between the best planes through the fluoroaryl ligand and the Dipp 2 Im phenyl substituents is 8.67(9) ° with a distance between the centroids of these two aromatic rings of 3.2402 Å (cf. 3.35 Å in graphite) [52] …”

Section: Resultsmentioning

confidence: 99%

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Föhrenbacher

Krahfuß

Zapf

et al. 2021

Chemistry A European J

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Fluoride abstraction from different types of transition metal fluoride complexes [LnMF] (M=Ti, Ni, Cu) by the Lewis acid tris(pentafluoroethyl)difluorophosphorane (C2F5)3PF2 to yield cationic transition metal complexes with the tris(pentafluoroethyl)trifluorophosphate counterion (FAP anion, [(C2F5)3PF3]−) is reported. (C2F5)3PF2 reacted with trans‐[Ni(iPr2Im)2(ArF)F] (iPr2Im=1,3‐diisopropylimidazolin‐2‐ylidene; ArF=C6F5, 1 a; 4‐CF3‐C6F4, 1 b; 4‐C6F5‐C6F4, 1 c) through fluoride transfer to form the complex salts trans‐[Ni(iPr2Im)2(solv)(ArF)]FAP (2 a‐c[solv]; solv=Et2O, CH2Cl2, THF) depending on the reaction medium. In the presence of stronger Lewis bases such as carbenes or PPh3, solvent coordination was suppressed and the complexes trans‐[Ni(iPr2Im)2(PPh3)(C6F5)]FAP (trans‐2 a[PPh3]) and cis‐[Ni(iPr2Im)2(Dipp2Im)(C6F5)]FAP (cis‐2 a[Dipp2Im]) (Dipp2Im=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were isolated. Fluoride abstraction from [(Dipp2Im)CuF] (3) in CH2Cl2 or 1,2‐difluorobenzene led to the isolation of [{(Dipp2Im)Cu}2]2+2 FAP− (4). Subsequent reaction of 4 with PPh3 and different carbenes resulted in the complexes [(Dipp2Im)Cu(LB)]FAP (5 a–e, LB=Lewis base). In the presence of C6Me6, fluoride transfer afforded [(Dipp2Im)Cu(C6Me6)]FAP (5 f), which serves as a source of [(Dipp2Im)Cu)]+. Fluoride abstraction of [Cp2TiF2] (7) resulted in the formation of dinuclear [FCp2Ti(μ‐F)TiCp2F]FAP (8) (Cp=η5‐C5H5) with one terminal fluoride ligand at each titanium atom and an additional bridging fluoride ligand.

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Section: Resultsmentioning

confidence: 99%

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Föhrenbacher

Krahfuß

Zapf

et al. 2021

Chemistry A European J

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“…These fluorinated building blocks can be introduced into other organic molecules. ,− A mechanism was proposed where, in the first step, the reaction of Ni(IMes) 2 ( 57 ) with the fluoroarene leads to an oxidative addition of the C–F bond with formation of trans -Ni(IMes) 2 F(Ar F ) ( 57a ; Scheme ). Although an initial “kinetic” C–H bond activation step would explain the regioselectivity of the borylation reaction (borylation occurs at a site adjacent to a hydrogen substituent), such a species could not be observed even at low temperatures.…”

Section: Nickel-catalyzed C–b Bond Formationmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon−boron bond into a carbon−X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row dblock transition metals have become increasingly widely used as catalysts for the formation of a carbon−boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon−boron bonds.

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“…Marder and Radius et al . reported that a combination of [Cu(OAc) 2 ] with phenanthroline effectively catalyzed the oxidative cross‐coupling of highly fluorinated aryl‐Bpin compounds with terminal alkynes under mild conditions [168] . The reaction of pentafluorophenyl‐Bpin with ethynylbenzene using 1.8 equivalents of Ag 2 O as the oxidant and 2 equivalents of K 3 PO 4 gave the homocoupled alkyne compound as the major product (Scheme 77).…”

Section: Applications Of Fluorinated Aryl Boronates In Organic Synthesismentioning

confidence: 99%

“… Optimization reaction of copper‐catalyzed oxidative cross‐coupling of fluorinated aryl‐Bpin with terminal alkynes [168] …”

Section: Applications Of Fluorinated Aryl Boronates In Organic Synthesismentioning

confidence: 99%

Fluorinated Aryl Boronates as Building Blocks in Organic Synthesis

et al. 2021

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Organoboron compounds are well known building blocks for many organic reactions. However, under basic conditions, polyfluorinated aryl boronic acid derivatives suffer from instability issues that are accelerated in compounds containing an ortho‐fluorine group, which result in the formation of the corresponding protodeboronation products. Therefore, a considerable amount of research has focused on novel methodologies to synthesize these valuable compounds while avoiding the protodeboronation issue. This review summarizes the latest developments in the synthesis of fluorinated aryl boronic acid derivatives and their applications in cross‐coupling reactions and other transformations.

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Copper‐Catalyzed Oxidative Cross‐Coupling of Electron‐Deficient Polyfluorophenylboronate Esters with Terminal Alkynes

Cited by 16 publications

References 121 publications

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

Tris(pentafluoroethyl)difluorophosphorane: A Versatile Fluoride Acceptor for Transition Metal Chemistry

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Fluorinated Aryl Boronates as Building Blocks in Organic Synthesis

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