Enantioselective Synthesis of Allylic Esters via Asymmetric Allylic Substitution with Metal Carboxylates Using Planar-Chiral Cyclopentadienyl Ruthenium Catalysts

Kanbayashi, Naoya; Onitsuka, Kiyotaka

doi:10.1021/ja908456b

Cited by 96 publications

(21 citation statements)

References 12 publications

(16 reference statements)

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“…Onitsuka et al have used planar-chiral ruthenium complex 216 ( Figure 10) to catalyze enantioselective allylic substitution reactions of allylic chlorides 226. [223][224][225] Alcohols, [223] sodium carboxylates, [224] and water [225] proved to be compatible nucleophiles, and afforded branched allylic ethers, esters, and alcohols, respectively (Scheme 99), with excellent enantiomeric excess and regioselectivity.…”

Section: Ruthenium-catalyzed Reactionsmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

2013

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Allylic alcohols represent an important and highly versatile class of chiral building blocks for organic synthesis. This Review summarizes the plethora of methods developed for the catalytic asymmetric synthesis of enantioenriched allylic alcohols. These include: dynamic kinetic resolution (DKR/DKAT), nucleophilic 1,2-addition to carbonyl groups, allylic substitution, oxidation of C-H bonds, the addition of O nucleophiles to π systems, reduction of unsaturated carbonyl compounds, and an alternative route from enantioenriched propargylic alcohols. Furthermore, these catalytic asymmetric processes are exemplified by their applications in the syntheses of complex molecules such as natural products and potential therapeutic agents.

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Section: Ruthenium-catalyzed Reactionsmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

2013

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“…Enantioenriched branched allyl esters are versatile precursors of branched allyl alcohols, which are valuable building blocks for the preparation of a wide range of biologically relevant organic molecules 25,26. There are a few reports that describe the catalytic asymmetric synthesis of allyl esters by utilization of sodium carboxylates with allyl carbonates/halides mediated by Pd‐BINAP catalysts27a or planar‐chiral cyclopentadienyl ruthenium catalysts 27b. Thus, the [COP‐OAc] 2 ‐catalyzed enantioselective substitution of ( Z )‐allyl imidates with carboxylic acids is a practical method for preparation of enantioenriched allyl esters 22,23…”

Section: Reactions Of Primary Allyl Trichloroacetimidates With Oxymentioning

confidence: 99%

Transition‐Metal‐Catalyzed Allylic Substitutions of Trichloroacetimidates

2014

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With the development of practical methods for their preparation, trichloroacetimidates have proven to be valuable substrates for use in carbohydrate and organic synthesis. The broad utility of allyl trichloroacetimidates for the construction of carbon‐heteroatom bonds is the result of the unique features of the trichloroacetimidate nitrogen functionality as a directing, nucleophilic, and leaving group. In this review we describe the expansion of Overman's [3,3]‐rearrangement of allyl trichloroacetimidates to allylic substitution reactions for regio‐ and enantioselective C–N, C–O, and C–F bond‐forming methodologies.

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“…verwendeten planar‐chirale Rutheniumkomplexe 216 (Abbildung 10), um enantioselektive allylische Substitutionsreaktionen von Allylchloriden 226 zu katalysieren 223–225. Alkohole,223 Natriumcarboxylate224 und Wasser225 erwiesen sich als kompatible Nucleophile und lieferten verzweigte Allylether, ‐ester bzw. ‐alkohole (Schema ) mit exzellenten Enantiomerenüberschüssen und Regioselektivitäten.…”

Section: Zugang üBer Stereoselektive C‐o‐bindungsknüpfungunclassified

Katalytische asymmetrische Synthese von Allylalkoholen und Allylalkohol‐Derivaten und deren Anwendung in der organischen Synthese

2013

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Allylalkohole sind eine wichtige und überaus nützliche Klasse chiraler Bausteine für die organische Synthese. Dieser Aufsatz fasst die Vielzahl an Methoden zur katalytischen asymmetrischen Synthese von enantiomerenangereicherten Allylalkoholen zusammen. Diese umfassen die dynamische kinetische Racematspaltung (DKR/DYKAT), 1,2‐Additionen von Nucleophilen an Carbonylgruppen, allylische Substitutionen, Oxidationen von C‐H‐Bindungen, die Addition von O‐Nucleophilen an π‐Systeme, die Reduktion von ungesättigten Carbonylverbindungen und eine alternative Syntheseroute ausgehend von enantiomerenangereicherten Propargylalkoholen. Darüber hinaus wird der präparative Nutzen dieser katalytischen asymmetrischen Transformationen jeweils am Beispiel ihrer Anwendung in der Synthese komplexer Moleküle wie z. B. Naturstoffen oder potenzieller Therapeutika gezeigt.

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Enantioselective Synthesis of Allylic Esters via Asymmetric Allylic Substitution with Metal Carboxylates Using Planar-Chiral Cyclopentadienyl Ruthenium Catalysts

Abstract: An asymmetric allylic substitution with sodium carboxylate using a planar-chiral cyclopentadienyl ruthenium complex has been developed. Optically active allylic esters were prepared in good yields with high regio- and enantioselectivities.

Cited by 96 publications

References 12 publications

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

Transition‐Metal‐Catalyzed Allylic Substitutions of Trichloroacetimidates

Katalytische asymmetrische Synthese von Allylalkoholen und Allylalkohol‐Derivaten und deren Anwendung in der organischen Synthese

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