Development of Zn–ProPhenol‐Catalyzed Asymmetric Alkyne Addition: Synthesis of Chiral Propargylic Alcohols

Trost, Barry M.; Bartlett, Mark J.; Weiss, Andrew H.; Wangelin, Axel Jacobi von; Chan, V. S.

doi:10.1002/chem.201202085

Cited by 64 publications

(27 citation statements)

References 141 publications

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“…[38] Nonetheless, a wide range of aromatic, a,bunsaturated, and aliphatic aldehydes 7 reacted with aryl, alkyl and silyl acetylenes in high yield and ee, as shown in Scheme 18. [39] In particular, trimethylsilyl acetylene and methyl propiolate gave excellent results (up to 97 % ee). Similar results were also obtained for product 66 f using only 1.5 equivalents of zinc reagents.…”

Section: Asymmetric Alkyne Additionmentioning

confidence: 98%

“…During reaction optimization, it was revealed that the alkynylation process generally required 2–3 equiv of dimethylzinc for high conversion and ee . Nonetheless, a wide range of aromatic, α,β‐unsaturated, and aliphatic aldehydes 7 reacted with aryl, alkyl and silyl acetylenes in high yield and ee , as shown in Scheme . In particular, trimethylsilyl acetylene and methyl propiolate gave excellent results (up to 97 % ee ).…”

Section: Catalytic Asymmetric Addition To Carbonylsmentioning

confidence: 99%

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Dinuclear Metal‐ProPhenol Catalysts: Development and Synthetic Applications

2019

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The ProPhenol ligand is a member of the chiral aza‐crown family that spontaneously forms a bimetallic complex upon treatment with alkyl metal reagents, such as Et2Zn and Bu2Mg. The resulting complex features Lewis acidic and Brønsted basic sites, enabling simultaneous activation of both nucleophile and electrophile in the same chiral environment. Since the initial report in 2000, metal‐ProPhenol catalysts have been used to facilitate a broad range of asymmetric transformations, including aldol, Mannich, and Henry reactions, as well as alkynylations and conjugation additions. By promoting such a diverse array of reactions, these complexes provide rapid and atom‐economical access to valuable complex building blocks. In this Review, we describe in detail the development and synthetic applications of these versatile catalysts with a special focus on recent efforts to improve reactivity and selectivity through ligand design and structural modification.

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Section: Asymmetric Alkyne Additionmentioning

confidence: 98%

Section: Catalytic Asymmetric Addition To Carbonylsmentioning

confidence: 99%

Dinuclear Metal‐ProPhenol Catalysts: Development and Synthetic Applications

2019

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“…Während der Reaktionsoptimierung wurde erkannt, dass der Alkinylierungsprozess generell 2–3 Äquivalente Dimethylzink für hohe Umsätze und ee ‐Werte erforderte . Dessen ungeachtet ließ sich ein breites Spektrum an aromatischen, α,β‐ungesättigten und aliphatischen Aldehyden 7 mit Aryl‐, Alkyl‐ und Silylacetylenen mit hohen Ausbeuten und ee ‐Werten umsetzen, wie dies in Schema gezeigt ist . Insbesondere Trimethylsilylacetylen und Methylpropiolat lieferten ausgezeichnete Ergebnisse (bis zu 97 % ee ).…”

Section: Katalytische Asymmetrische Addition An Carbonyleunclassified

“…[38] Dessen ungeachtet ließ sich ein breites Spektrum an aromatischen, a,b-ungesättigten und aliphatischen Aldehyden 7 mit Aryl-, Alkyl-und Silylacetylenen mit hohen Ausbeuten und ee-Werten umsetzen, wie dies in Schema 18 gezeigt ist. [39] Insbesondere Trimethylsilylacetylen und Methylpropiolat lieferten ausgezeichnete Ergebnisse (bis zu 97 % ee). ¾hnliche Ergebnisse wurden auch für das Produkt 66 f bei Einsatz von nur 1.5 ¾quivalenten Zinkreagenz erhalten.…”

Section: Asymmetrische Alkin-additionunclassified

Zweikernige Metall‐ProPhenol‐Katalysatoren: Entwicklung und Anwendungen in der Synthese

2019

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ProPhenol‐Moleküle gehören zur Gruppe der chiralen Azakronen‐Verbindungen und bilden bei Umsetzung mit Alkylmetall‐Reagenzien wie Et2Zn und Bu2Mg spontan einen bimetallischen Komplex. Dieser Komplex hat Lewis‐saure und Brønsted‐basische Reaktionszentren, die eine simultane Aktivierung eines Nukleophils und eines Elektrophils in derselben chiralen Umgebung erlauben. Seit dem ersten Bericht im Jahr 2000 haben Metall‐ProPhenol‐Katalysatoren eine große Bandbreite asymmetrischer Umwandlungen wie Aldol‐, Mannich‐ und Henry‐Reaktionen sowie Alkinylierungen und konjugierte Additionen ermöglicht. Aufgrund der vielfältigen Einsatzmöglichkeiten bei unterschiedlichen Reaktionen erlauben diese Komplexe einen schnellen und atomökonomischen Zugang zu wertvollen komplexen Baugruppen. In diesem Aufsatz beschreiben wir detailliert die Entwicklung und synthetischen Anwendungen dieser vielseitigen Katalysatoren, mit besonderem Blick auf kürzliche Bemühungen, Reaktivität und Selektivität durch Ligandendesign und strukturelle Veränderungen zu verbessern.

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“…After filtration, the solvent was removed in a rotary evaporator, to give 55% of a yellow oil. [31]. Isano oil (0.15 gr) and Adam's catalyst (5 mol%) were mixed in ethyl acetate (50 mL).…”

Section: Extraction Of Oilmentioning

confidence: 99%

Physicochemical Properties of Diacetylenic Light Fuel Oil from Congolese Oleaginous Plant Ongokea gore (Hua) Pierre

Ntumba

Mulula

Kashishi

et al. 2017

Journal of Applied Chemistry

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Vegetable oil-based fuels are promising alternative fuels for diesel and light fuel engines because of their environmental and economic strategic advantages. In this study, Ongokea gore oil (OGO) and its fully hydrogenated oil were transesterified by means of ethanol in the presence of sodium ethoxide. Fatty acid ethyl esters (FAEE) products were confirmed by 1 H NMR and characterized by physical-chemical methods in accordance with the ASTM D 6751 and AFNOR M 15-009 specifications for biodiesels and light biofuels. These methods concern determination of color, density, viscosity, flash and pour points, ash, water and sulfur contents, and corrosion on copper. It was found that pure fatty acid ethyl esters of Ongokea gore oil (B100) and its hydrogenated oil (B100-H) meet standard requirements for most of the biodiesel characteristics studied. Only the kinematic viscosity and density values were outside recommended biodiesel standard limits which makes them unsuitable for use in diesel engines. In accordance with the AFNOR M 15-009 specifications of light fuels, they can be used in light fuel engines. Physical-chemical properties of B20, a FAEE blend in petrodiesel, are within the limits prescribed for petrodiesel standards. In brief, Ongokea gore seeds, a nonedible and high-oil-producing feedstock, are suitable starting material for production of light biofuel. The latter blends in petrodiesel can be used as fuel in diesel engines.

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Development of Zn–ProPhenol‐Catalyzed Asymmetric Alkyne Addition: Synthesis of Chiral Propargylic Alcohols

Cited by 64 publications

References 141 publications

Dinuclear Metal‐ProPhenol Catalysts: Development and Synthetic Applications

Dinuclear Metal‐ProPhenol Catalysts: Development and Synthetic Applications

Zweikernige Metall‐ProPhenol‐Katalysatoren: Entwicklung und Anwendungen in der Synthese

Physicochemical Properties of Diacetylenic Light Fuel Oil from Congolese Oleaginous Plant Ongokea gore (Hua) Pierre

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