Sodium Phenoxide−Phosphine Oxides as Extremely Active Lewis Base Catalysts for the Mukaiyama Aldol Reaction with Ketones

Hatano, Manabu; Takagi, Erina; Ishihara, Kazuaki

doi:10.1021/ol702052r

Cited by 72 publications

(40 citation statements)

References 16 publications

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“…[40] Diese thermodynamische Präferenz der Retro-Aldolreaktion ist im Falle von Silylketenacetalen als Donoren effektiv umgekehrt, und die Gruppen von Denmark und später von Kanai und Shibasaki entwickelten enantioselektive Lewis-Basen-katalysierte Additionsreaktionen von Tr ichlorsilylketenacetalen [41] und Cu I -katalysierte Additionen eines Tr imethylsilylketenacetals an Ketone. B. Ester-)Enolaten typischerweise thermodynamisch ungünstig sind.…”

Section: Angewandte Chemieunclassified

IDPi‐Katalyse

2019

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Hohe Acidität und sterische Einschränkung sind Schlüsselelemente bei der asymmetrischen Säure‐Katalyse. Die kürzlich eingeführten Imidodiphosphorimidat (IDPi)‐Brønsted‐Säuren haben diese Eigenschaften mit bemerkenswertem Erfolg kombiniert. Sie wirken als hochaktive Brønsted‐Säure‐Katalysatoren und als “Silylium”‐Lewis‐Säure‐Präkatalysatoren bei zahlreichen vorher nicht zugänglichen Transformationen. Schwierig zu aktivierende Substrate wie einfache Olefine ließen sich leicht umsetzen. Ketone wurden als Akzeptoren bei Aldolreaktionen eingesetzt, die eine Katalyse im Sub‐ppm‐Bereich ermöglichten, während Enolate des kleinsten Donoraldehyds, Acetaldehyd, nicht polymerisiert, sondern gezielt ein einziges Mal an eine Vielzahl von Akzeptoraldehyden gekuppelt wurden.

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Section: Angewandte Chemieunclassified

IDPi‐Katalyse

2019

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“…With 10 mol% each of alkali metal phenoxides and phosphine oxides in this aldol reaction, PhONa showed the best reactivity in the presence of 1,2-(O=PPh 2 ) 2 C 4 H 4. Even with 0.5 mol% of catalyst 70, a desired product was obtained in excellent yield (97%) (124). Later, the authors further developed a highly efficient Mukaiyama aldol reaction between ketones and trimethylsilyl enolates in the presence of catalytic potassium alkoxidecrown ether complexes, which gave the desired products in excellent yields (>99% yield in most cases) (125).…”

Section: Main Group Metals-base Catalystsmentioning

confidence: 99%

Aldol Reaction—Homogeneous

Cai

2011

Encyclopedia of Catalysis

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The aldol reaction is one of the oldest and important methods for the construction of carbon–carbon bonds in organic chemistry. Over the last 30 years, tremendous efforts have resulted in the development of many highly sophisticated and efficient catalytic methods of modern aldol reactions in catalytic chemo‐, regio‐, enantio‐, and diastereoselective manners. This review outlined those efforts in homogeneous catalysis and discussed with selected examples (331 publications) according to the different elemental types of catalysts, for example, transition metals and rare earth metals based Lewis acids, main group metals based catalysts, multifunctional catalysts, and metal‐free catalysts.

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“…[27] In the presence of sodium phenoxide and 1,2-(O=PPh 2 ) 2 C 6 H 4 (Ͻ 1 mol-%, each), diaryl ketones reacted smoothly at -78°C in THF to give the corresponding aldol products high yield. [27] In the presence of sodium phenoxide and 1,2-(O=PPh 2 ) 2 C 6 H 4 (Ͻ 1 mol-%, each), diaryl ketones reacted smoothly at -78°C in THF to give the corresponding aldol products high yield.…”

Section: Lewis Base Catalyzed Reaction With Trichlorosilyl Ketene Acementioning

confidence: 99%

Catalytic Enantioselective Aldol Additions to Ketones

Adachi

Harada

2009

Eur J Org Chem

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Enantioselective aldol addition to ketones has received growing attention since the resulting tertiary aldols are valuable building blocks for many biologically active compounds. Recently, several catalytic methodologies have been developed based on the activation of acceptor ketones and/or nucleophile enolates, overcoming problems associated with the lower reactivity and decreased steric discrimination of ketones compared to aldehydes. This microreview presents an overview of the progresses in the catalytic enantioselective aldol additions to ketones. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Sodium Phenoxide−Phosphine Oxides as Extremely Active Lewis Base Catalysts for the Mukaiyama Aldol Reaction with Ketones

Cited by 72 publications

References 16 publications

IDPi‐Katalyse

IDPi‐Katalyse

Aldol Reaction—Homogeneous

Catalytic Enantioselective Aldol Additions to Ketones

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