A New Synthesis of α-Alkoxy Ketones<sup>1</sup>

Newman, Melvin S.; Beal, P. F.

doi:10.1021/ja01167a100

Cited by 71 publications

(19 citation statements)

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“…Earlier in 1952, Yates noted that reaction of a-diazoketones and alcohols in the presence of Cu powder gave only a-alkoxy ketone products resulting from carbene O À H insertion, instead of esters by the Wolff rearrangement, and proposed the formation of an a-ketocarbene intermediate bound to the Cu surface with the valence electrons completing the octet of the carbenic carbon atom. [9] This sensible explanation was followed by many publications claiming the reactive species had a carbene/Cu bond. [10] Hammond, however, postulated the possibility of the intervention of a charge-transfer complex between triplet CH 2 and Cu powder or soluble Fe III tris(dipivaloylmethide).…”

Section: The Birth Of Organometallic Asymmetric Catalysismentioning

confidence: 97%

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Noyori

2012

Angew Chem Int Ed

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As Louis Pasteur said, "Chance favors only a prepared mind." Serendipitous events reorienting the pathway of science often occur through the actions of dedicated individuals with unique cultural and educational backgrounds, an original sense of values, and firm principles. Science is the fountainhead of human knowledge and possesses an indispensable cultural value. Science-based technologies and the innovations derived from them are the foundation of the civilized society in which we live today. All scientific endeavors begin with observations, or facts. However, the real goal of research activity is to convert accumulated knowledge to something with new technological, economic, or social value. Innovation is an essential aspect to assure the continued survival of humanity. And often, as my half-century of research reflects, the act of turning facts into values is facilitated by dialogue. Thus, to acquire the necessary combined wisdom, scientists must have ongoing conversations with the societies they serve, as well as with their counterparts in other nations.

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Section: The Birth Of Organometallic Asymmetric Catalysismentioning

confidence: 97%

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Noyori

2012

Angew Chem Int Ed

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“…[4] Diese asymmetrische Cyclopropanierung verlief zwar mit niedriger Enantioselektivität, lieferte aber das allgemeine Prinzip der asymmetrischen Katalyse, das heute in Forschung und Industrie breite Anwendung findet (Abbildung 1). [5][6][7] [9] Dieser sinnvollen Erklärung folgten viele Publikationen, in denen behauptet wurde, die reaktive Spezies hätte eine Carben/Cu-Bindung. [10] Hammond postulierte hingegen die mçgliche Beteiligung eines Charge-Transfer-Komplexes zwischen Triplett-CH 2 und Cu-Pulver oder lçslichem Fe III -Tris(dipivaloylmethid).…”

Section: Die Geburt Der Asymmetrischen Organometallkatalyseunclassified

Fakten sind der Feind der Wahrheit – Betrachtungen über Zufallsentdeckungen und ungeahnte Entwicklungen der asymmetrischen Katalyse

Noyori

2012

Angewandte Chemie

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“Der Zufall begünstigt nur den vorbereiteten Geist”, sagte Louis Pasteur. Zufallsereignisse, die dem Weg der Wissenschaft eine neue Richtung geben, geschehen oft infolge von Handlungen passionierter Individuen mit unverwechselbarem kulturellen und erzieherischen Hintergrund, einem ursprünglichen Wertempfinden und festen Prinzipien. Wissenschaft ist die Quelle menschlichen Wissens und besitzt einen unverzichtbaren kulturellen Wert. Wissenschaftsbasierte Technologien und die aus ihnen abgeleiteten Innovationen sind die Grundlage der zivilisierten Gesellschaft, in der wir heute leben. Alle wissenschaftlichen Bestrebungen beginnen mit Beobachtungen oder Fakten. Das eigentliche Ziel der Forschungsaktivität ist es aber, das gesammelte Wissen in etwas umzuwandeln, das neuen technologischen, ökonomischen oder sozialen Wert hat. Innovation ist ein entscheidender Aspekt, der den Fortbestand der Menschheit gewährleistet. Und wie die 50 Jahre meiner Forschung zeigen, wird das Umwandeln von Fakten in Werte durch den Dialog erleichtert. Wissenschaftler können die notwendige Gesamterfahrung nur erwerben, wenn sie in laufendem Gespräch mit den Gesellschaften, in deren Dienst sie stehen, sowie mit ihren Kollegen in anderen Nationen bleiben.

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“…Traditionally, the installation of alkoxy substituents at the carbonyl a-position can be accomplished through multistep processes via synthetic intermediates such as silyl enol ethers, [3] enol acetates [4] or a-diazo ketones. [5] These methods suffer from the inconvenient multiple oxidation procedures or rigorous control of the reaction conditions. Moreover, the substrate scope of these methods is limited as the introduction of a long-chain alkoxy group remains underdeveloped.…”

Section: Introductionmentioning

confidence: 99%

Sodium Iodide‐Catalyzed Direct α‐Alkoxylation of Ketones with Alcohols via Oxidation of α‐Iodo Ketone Intermediates

et al. 2015

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Abstract:The direct a-alkoxylation of ketones with alcohols via a sodium iodide-catalyzed oxidative cross-coupling has been developed. This protocol enables a range of alkyl aryl ketones to crosscouple with an array of alcohols in synthetically useful yields. The mechanistic studies provided solid evidence supporting that an a-iodo ketone was a key reaction intermediate, being converted into an a-alkoxylated ketone via further oxidation to a hypervalent iodine species rather than a common nucleophilic substitution, and was generated from the ketone starting material via a radical intermediate. These new mechanism insights should have an effect on the design of iodide-catalyzed oxidative cross-coupling reactions between nucleophiles.

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A New Synthesis of α-Alkoxy Ketones¹

Cited by 71 publications

References 0 publications

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Fakten sind der Feind der Wahrheit – Betrachtungen über Zufallsentdeckungen und ungeahnte Entwicklungen der asymmetrischen Katalyse

Sodium Iodide‐Catalyzed Direct α‐Alkoxylation of Ketones with Alcohols via Oxidation of α‐Iodo Ketone Intermediates

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A New Synthesis of α-Alkoxy Ketones1

Cited by 71 publications

References 0 publications

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Facts are the Enemy of Truth—Reflections on Serendipitous Discovery and Unforeseen Developments in Asymmetric Catalysis

Fakten sind der Feind der Wahrheit – Betrachtungen über Zufallsentdeckungen und ungeahnte Entwicklungen der asymmetrischen Katalyse

Sodium Iodide‐Catalyzed Direct α‐Alkoxylation of Ketones with Alcohols via Oxidation of α‐Iodo Ketone Intermediates

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A New Synthesis of α-Alkoxy Ketones¹