Catalysis of Intramolecular Morita–Baylis–Hillman and Rauhut–Currier Reactions by Fluorous Phosphines; Facile Recovery by Liquid/Solid Organic/Fluorous Biphase Protocols Involving Precipitation, Teflon<sup>®</sup> Tape, and Gore‐Rastex<sup>®</sup> Fiber

Seidel, Florian; Gladysz, J. A.

doi:10.1002/adsc.200800403

Cited by 67 publications

(19 citation statements)

References 37 publications

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“…In 2002, Krische and co‐workers22, 23 and Roush and co‐workers24 reported the intramolecular RC reaction of symmetrical and unsymmetrical bis(enone) substrates using trialkylphosphines. Gladysz et alreported the RC reaction involving bis(thioesters) using a fluorinated phosphine catalyst 25…”

Section: Introductionmentioning

confidence: 99%

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Chen

Song

et al. 2014

Chemistry A European J

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Rh(III) -catalyzed N-nitroso-directed CH addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful CH functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.

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Section: Introductionmentioning

confidence: 99%

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Chen

Song

et al. 2014

Chemistry A European J

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“…Gladysz et alreported the RC reaction involving bis(thioesters) using a fluorinated phosphine catalyst. [25] In 2007, thiol/thiolate catalysis of this reaction was disclosed. [8,9,26] Among these disclosures, enantioselective RC reactions using a simple cysteine derivative as an asymmet-ric catalyst were discovered.…”

Section: Introductionmentioning

confidence: 99%

The Roles of Counterion and Water in a Stereoselective Cysteine‐Catalyzed Rauhut–Currier Reaction: A Challenge for Computational Chemistry

Osuna¹,

Dermenci²,

Miller³

et al. 2013

Chemistry A European J

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The stereoselective Rauhut-Currier (RC) reaction catalyzed by a cysteine derivative has been explored computationally with DFT (M06-2X) theory. Both methanethiol and a chiral cysteine derivative were studied as nucleophiles. The complete reaction pathway involves rate-determining elimination of the thiol catalyst from the Michael addition product. The stereoselective Rauhut-Currier reaction, catalyzed by a cysteine derivative as nucleophile, has also been studied in detail. This reaction was experimentally found to be extremely sensitive to the reaction conditions, such as the number of water equivalents and the effect of potassium counterion. The E1cB process for catalyst elimination has been explored computationally for the 8 possible stereoisomers. The effect of explicit water solvation and the presence of counterion (either K+ or Na+) has been studied for the lowest energy enantiomer pair (1S, 2R, 3S)/(1R, 2S, 3R).

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“…The fluorous phosphine ligand used, for example, in a Morita-Baylis-Hillman reaction, can be removed by adsorption on poly(tetrafluoroethylene) (PTFE, Teflon), either as Teflon tape or Gore-Rastex fibers, and coprecipitation together with them [29] (Scheme 6.7).…”

Section: Fluorous Biphase Catalysis 215mentioning

confidence: 99%

“…). The fluorous phosphine catalyst for a Morita-Baylis-Hill reaction can be fully recovered by adsorption to PTFE, most effectively as high surface area Gore-Rastex TM fibers[29].…”

mentioning

confidence: 99%

Fluorous Chemistry

Kirsch

2013

Modern Fluoroorganic Chemistry

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Catalysis of Intramolecular Morita–Baylis–Hillman and Rauhut–Currier Reactions by Fluorous Phosphines; Facile Recovery by Liquid/Solid Organic/Fluorous Biphase Protocols Involving Precipitation, Teflon^® Tape, and Gore‐Rastex^® Fiber

Cited by 67 publications

References 37 publications

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

The Roles of Counterion and Water in a Stereoselective Cysteine‐Catalyzed Rauhut–Currier Reaction: A Challenge for Computational Chemistry

Fluorous Chemistry

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Catalysis of Intramolecular Morita–Baylis–Hillman and Rauhut–Currier Reactions by Fluorous Phosphines; Facile Recovery by Liquid/Solid Organic/Fluorous Biphase Protocols Involving Precipitation, Teflon® Tape, and Gore‐Rastex® Fiber

Cited by 67 publications

References 37 publications

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

The Roles of Counterion and Water in a Stereoselective Cysteine‐Catalyzed Rauhut–Currier Reaction: A Challenge for Computational Chemistry

Fluorous Chemistry

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Product

Resources

About

Catalysis of Intramolecular Morita–Baylis–Hillman and Rauhut–Currier Reactions by Fluorous Phosphines; Facile Recovery by Liquid/Solid Organic/Fluorous Biphase Protocols Involving Precipitation, Teflon^® Tape, and Gore‐Rastex^® Fiber