Carbonylation of acetylenes under water gas shift conditions: a new method for synthesis of furan-2(5H)-ones

Doyama, Kazuo; Joh, Takashi; Onitsuka, Kiyotaka; Shiohara, T.; Takahashi, Shigetoshi

doi:10.1039/c39870000649

Cited by 26 publications

(28 citation statements)

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“…[179] A mechanistic proposal was then put forward which proceeds by double carbonylation of the alkyne and rearrangement to form xxxviii , generation of a Rh-hydride intermediate xl via WGSR, and subsequent reductive elimination to the product (Scheme 15). [182] …”

Section: The Water-gas Shift Reaction In Organic Synthesismentioning

confidence: 99%

“…Ther eductive cyclocarbonylation under WGSR conditions was pioneered and considerably developed by Takahashi and co-workers.I na ni nitial report, the reaction of internal alkynes with CO and Rh 4 (CO) 12 under basic conditions afforded furanones (Figure 13 a). [179] Thereaction was subsequently extended to terminal alkynes under modified conditions (Figure 13 b). [180] This pathway is ap rerogative of the CO/H 2 Os ystem, as the use of CO/H 2 caused hydrogenation of the alkyne and hydrohydroxymethylation.…”

Section: Other Carbonylation Reactionsmentioning

confidence: 99%

“…[182] Theinvolvement of the WGSR as the source of reducing equivalents was initially established by carrying out the reaction with D 2 O, which resulted in full incorporation of Dat the 5-position of the furanone. [179] Amechanistic proposal was then put forward which proceeds by double carbonylation of the alkyne and rearrangement to form xxxviii,g eneration of aR h-hydride intermediate xl via WGSR, and subsequent reductive elimination to the product (Scheme 15). [182] Similar approaches to the synthesis of furanones were also described by other research groups,u sing PdI 2 , [183] Co 2 Rh 2 / C, [184] and Ru 3 (CO) 12 .…”

Section: Angewandte Chemiementioning

confidence: 99%

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Harnessing the Power of the Water‐Gas Shift Reaction for Organic Synthesis

Ambrosi

Denmark

2016

Angew Chem Int Ed

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Since its original discovery over a century ago, the water-gas shift reaction (WGSR) has played a crucial role in industrial chemistry, providing a source of H2 to feed fundamental industrial transformations such as the Haber–Bosch synthesis of ammonia. Although the production of hydrogen remains nowadays the major application of the WGSR, the advent of homogeneous catalysis in the 1970s marked the beginning of a synergy between WGSR and organic chemistry. Thus, the reducing power provided by the CO/H2O couple has been exploited in the synthesis of fine chemicals; not only hydrogenation-type reactions, but also catalytic processes that require a reductive step for the turnover of the catalytic cycle. Despite the potential and unique features of the WGSR, its applications in organic synthesis remain largely underdeveloped. The topic will be critically reviewed herein, with the expectation that an increased awareness may stimulate new, creative work in the area.

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Section: The Water-gas Shift Reaction In Organic Synthesismentioning

confidence: 99%

Section: Other Carbonylation Reactionsmentioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

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Harnessing the Power of the Water‐Gas Shift Reaction for Organic Synthesis

Ambrosi

Denmark

2016

Angew Chem Int Ed

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“…[178] 12 unter basischen Bedingungen zu Furanonen (Abbildung 13 a). [179] Später wurde die Reaktion unter modifizierten Bedingungen auf terminale Alkine angewendet (Abbildung 13 b). [180] Dieser Reaktionsweg ist dem CO/H 2 O-System vorbehalten, denn mit CO/H 2 erfolgen die Hydrierung des Alkins und die Hydrohydroxymethylierung.…”

Section: Andere Carbonylierungsreaktionenunclassified

Die Wassergas‐Shift‐Reaktion in der organischen Synthese

Ambrosi

Denmark

2016

Angewandte Chemie

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Seit ihrer Entdeckung vor mehr als hundert Jahren hat die Wassergas‐Shift‐Reaktion (WGSR) entscheidende Bedeutung in der industriellen Chemie, indem sie den Wasserstoff zur Beschickung grundlegender großtechnischer Prozesse wie der Haber‐Bosch‐Synthese von Ammoniak liefert. Obwohl die Produktion von Wasserstoff immer noch die Hauptanwendung der WGSR ist, markierte die Einführung der homogenen Katalyse in den 1970er Jahren den Beginn einer Synergie zwischen der WGSR und der organischen Chemie. Dabei wurde das Reduktionsvermögen des CO/H2O‐Paars in der Synthese von Feinchemikalien nicht nur für Hydrierungsreaktionen genutzt, sondern auch für katalytische Prozesse, deren Umsatz einen Reduktionsschritt im Katalysezyklus erfordert. Ungeachtet des Potenzials und der einzigartigen Eigenschaften der WGSR sind ihre Anwendungen in der organischen Synthese bisher noch wenig entwickelt. Dieses Thema wird hier kritisch besprochen in der Hoffnung, dass eine erhöhte Wahrnehmung zu neuen, kreativen Arbeiten auf dem Gebiet anregt.

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“…In 1990, Takahashi and co-workers found that the use of water instead of molecular hydrogen can give cyclocarbonylated products, 2(5H )-furanones, in excellent yield [12][13][14]. Later on, a novel rhodium-catalyzed carbonylation of [15].…”

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confidence: 96%