Fluorous Biphasic Catalysis: Complexation of 1,4,7‐[C8F17(CH2)3]3‐1,4,7‐Triazacyclononane with [M(C8F17(CH2)2CO2)2] (M = Mn, Co) To Provide Perfluoroheptane‐Soluble Catalysts for Alkane and Alkene Functionalization in the Presence of t‐BuOOH and O2

Vincent, Jean‐Marc; Rabion, Alain; Yachandra, Vittal K.; Fish, Richard H.

doi:10.1002/anie.199723461

Cited by 157 publications

(46 citation statements)

References 9 publications

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“…So far, a number of reactions have been successfully evaluated under FBS conditions, including hydroformylation [4], hydroboration [5], hydrosilylation [6], epoxidation [7] [8], and the Rh-catalyzed cyclopropanation of alkenes [9], oxidations of aldehydes [7], thioesters [7], and alkanes [10], as well as Wacker oxidations [11], Pdcatalyzed allylic substitutions [12], and Negishi [13] and Heck reactions [14].…”

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confidence: 99%

Application of the Fluorous-Biphase Concept to Palladium-Catalyzed Sonogashira Couplings

Märkert

Bannwarth

2002

HCA

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Dedicated to Professor Wolfgang Pfleiderer on the occasion of his 75th birthday Sonogashira C,C couplings in a fluorous biphasic system by application of three differently perfluorotagged Pd complexes are reported. All three complexes were probed in the coupling of four bromoarenes to three alkynes. The parallel workup procedure allowed for straightforward product isolation and catalyst recovery by simple extraction steps. In particular, the coupling of electron-deficient bromoarenes proceeded with good yields and allowed for the catalyst to be used up to three times.1. Introduction. ± According to the alchemists rule similia similibus solvuntur, highly fluorinated compounds show greatly enhanced solubility in perfluorinated alkanes even in the presence of a second organic phase. This principle can be applied in catalytic processes as well as in combinatorial strategies. Horva¬th and Ra¬bai [1] were the first to point out that this allows for a perfluoro-tagged catalyst to remain in the fluorous phase, while other reactants dissolve in the organic phase. Furthermore, the temperature-dependent miscibility of such fluorous biphasic systems (FBS) [2] provides an option to homogenize the phases at elevated temperatures. Workup is essentially straightforward, as the two phases reform after lowering the temperature again. Simple phase-separation suffices to recover the perfluoro-tagged catalyst. At the same time, product isolation can be reduced to an extraction protocol.Syntheses in the nonpolar reaction medium scCO 2 represent a further application of perfluoro-tags where they can be used to mediate sufficient solubility [3]. Hence, there is currently a great deal of interest in perfluoro-tagged catalysts. So far, a number of reactions have been successfully evaluated under FBS conditions, including hydroformylation [4], hydroboration [5], hydrosilylation [6], epoxidation [7] [8], and the Rh-catalyzed cyclopropanation of alkenes [9], oxidations of aldehydes [7], thioesters [7], and alkanes [10], as well as Wacker oxidations [11], Pdcatalyzed allylic substitutions [12], and Negishi [13] and Heck reactions [14].Among the transition-metal catalyzed reactions, C,C couplings are of particular importance, as they allow construction of molecule skeletons. We have previously reported on highly efficient protocols for Stille [15] and Suzuki [16] cross-coupling

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confidence: 99%

Application of the Fluorous-Biphase Concept to Palladium-Catalyzed Sonogashira Couplings

Märkert

Bannwarth

2002

HCA

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“…[11] It was thus realized that, besides a relatively high fluorine loading, the presence of more than two fluoroponytails was crucial for ensuring a suitable degree of fluorophilicity to the CE derivatives. To this end, dibenzo-18-crown-6 ether (DB18-C-6) was an ideal scaffold, due to the ease of controlled functionalization of its aromatic moieties, and to their possible shielding effect towards the electron-withdrawing effect of perfluoroalkyl substituents, which could significantly reduce the Lewis basicity of the oxygen binding sites, and thus the utility of the resulting fluoroponytailed CE as a PT catalyst.…”

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confidence: 99%

Perfluorocarbon Soluble Crown Ethers as Phase Transfer Catalysts

2008

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Fluorous derivatives of dibenzo-18-crown-6 ether were readily prepared by means of metal-catalyzed cross-coupling reactions, and then successfully applied as catalysts in representative solid-liquid phase transfer catalysis (PTC) reactions, which were performed in standard organic solvents, such as chlorobenzene and toluene, and also in fluorous solvents, such as perfluoro-1,3-dimethylcyclohexane (PFDMC). It was clearly shown that properly designed fluoroponytailed crown ethers can promote the disintegration of the crystal lattice of alkali salts and transfer anions from the solid surface into an apolar, non-coordinating perfluorocarbon phase. Far from being a simple chemical curiosity, this unprecedented observation has relevant implications in the design of PTC scenarios of wide applicability. This new paradigm represents an advance in crown ether chemistry, and their use as recyclable phase transfer catalysts.

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“…The first Journal of Fluorine Chemistry 125 (2004) 721-724 step proceeded by a free radical addition of a perfluorooctyl iodide (CF 3 (CF 2 ) 7 I) to allyl alcohol that was initiated with AIBN to provide the perfluoroalkylated iodohydrin 1 in 75% yield. Compound 1 was then reduced to the perfluoroalkyl alcohol 2 in 75% yield by using tributyltin hydride [8]. Oxidation of 2 with Jone's oxidation agent gave acid 3 in 90% yield.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and surface antimicrobial activity of a novel perfluorooctylated quaternary ammonium silane coupling agent

Shao

Meng

Qing

2004

Journal of Fluorine Chemistry

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Fluorous Biphasic Catalysis: Complexation of 1,4,7‐[C₈F₁₇(CH₂)₃]₃‐1,4,7‐Triazacyclononane with [M(C₈F₁₇(CH₂)₂CO₂)₂] (M = Mn, Co) To Provide Perfluoroheptane‐Soluble Catalysts for Alkane and Alkene Functionalization in the Presence of t‐BuOOH and O₂

Abstract: COMMUNICATIONS 20 steps, and the overall yield is 0.65% starting from D-( +)mannitol. The synthetic route features regioselective macrolactonization of a disaccharide bearing a 19-membered ring and a one-pot glycosidation for construction of a macrolactone tetrasaccharide.

Cited by 157 publications

References 9 publications

Application of the Fluorous-Biphase Concept to Palladium-Catalyzed Sonogashira Couplings

Application of the Fluorous-Biphase Concept to Palladium-Catalyzed Sonogashira Couplings

Perfluorocarbon Soluble Crown Ethers as Phase Transfer Catalysts

Synthesis and surface antimicrobial activity of a novel perfluorooctylated quaternary ammonium silane coupling agent

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