Regiodivergent Ligand‐Controlled Rhodium‐Catalyzed [(2+2)+2] Carbocyclization Reactions with Alkyl Substituted Methyl Propiolates

Evans, P. Andrew; Sawyer, James R.; Inglesby, Phillip A.

doi:10.1002/ange.201002117

Angewandte Chemie

2010

DOI: 10.1002/ange.201002117

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Regiodivergent Ligand‐Controlled Rhodium‐Catalyzed [(2+2)+2] Carbocyclization Reactions with Alkyl Substituted Methyl Propiolates

P. Andrew Evans

James R. Sawyer

Phillip A. Inglesby

Abstract: Man hat die Wahl: In der Titelreaktion lässt sich die selektive Bildung der zwei Regioisomere durch sorgfältige Wahl der Hilfsliganden steuern (siehe Schema). Entscheidend war der Befund, dass Reste von Silbersalzen aus der Salzmetathese des neutralen Komplexes einen starken Einfluss auf die Regio‐ und Diastereoselektivität haben.

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Cited by 20 publications

References 27 publications

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Dithiolane‐Directed Tandem Oxidation/1,2‐Benzyl Migration of Tetramic Acids under Ambient Conditions

Xia

et al. 2012

Adv Synth Catal

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Reactions directly involving triplet oxygen are an important issue in organic and biological chemistry. We now report that exposure of tetramic acids in the open air (molecular oxygen) at room temperature can lead to the formation of succinimide derivatives in high to excellent yields via tandem oxidation/1,2‐benzyl migration. In this reaction, the dithiolane moiety plays a crucial role and succinimides are produced either in the presence or absence of dibutyl sulfide as reductant.

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Dithiolane‐Directed Tandem Oxidation/1,2‐Benzyl Migration of Tetramic Acids under Ambient Conditions

Xia

et al. 2012

Adv Synth Catal

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Copper‐Catalyzed Cascade Cyclization Reactions of Isocyanides with α‐Diazocarbonyls as N‐Terminal Electrophiles: Efficient Synthesis of 2‐Imidazolines and 1,1′‐Biimidazoles

et al. 2016

Adv Synth Catal

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The reactions of α‐diazocarbonyls have been extensively studied and widely applied in organic synthesis acting as 1,3‐dipoles, metal carbene precursors and C‐nucleophiles. However, the utility of the electrophilic capability of their terminal nitrogen has been a challenging problem. Herein, a novel copper‐catalyzed cascade cyclization reaction of isocyanides with α‐diazocarbonyls as N‐terminal electrophiles has been developed for the first time. The reaction involves a sequential intermolecular nucleophilic addition/[3+2] cycloaddition/intramolecular cyclization‐ring‐opening/elimination procedure and provides a new and efficient method for the construction of imidazolines and biimidazoles in a single step from readily available starting materials under very mild conditions.magnified image

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Enantioselective Construction of 5‐6‐5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes

et al. 2021

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Herein, we report a Rh-catalyzed asymmetric [2 + 2 + 2] cycloaddition of ene-yne-yne enediynes to generate enantio-enriched tricyclic cyclohexadienes bearing a quaternary bridgehead carbon. We found that the Rh-Phanephos complex is an appropriate catalyst for the cycloaddition of enediynes bearing an unsubstituted propiolate terminus, whereas Rh-biaryl bisphosphine catalysts, which have been widely used for asymmetric cycloadditions of alkynes and alkenes, are not applicable for the reaction of such enediynes. Several control experiments suggest that the reaction using the Rh-Phanephos complex exclusively proceeds via a rhodacyclopentadiene intermediate, unlike when using a Rh-biaryl bisphosphine complex that can form a rhodacyclopentadiene intermediate as well as a rhodacyclopentene intermediate in a substratedependent manner.

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Regiodivergent Ligand‐Controlled Rhodium‐Catalyzed [(2+2)+2] Carbocyclization Reactions with Alkyl Substituted Methyl Propiolates

Cited by 20 publications

References 27 publications

Dithiolane‐Directed Tandem Oxidation/1,2‐Benzyl Migration of Tetramic Acids under Ambient Conditions

Dithiolane‐Directed Tandem Oxidation/1,2‐Benzyl Migration of Tetramic Acids under Ambient Conditions

Copper‐Catalyzed Cascade Cyclization Reactions of Isocyanides with α‐Diazocarbonyls as N‐Terminal Electrophiles: Efficient Synthesis of 2‐Imidazolines and 1,1′‐Biimidazoles

Enantioselective Construction of 5‐6‐5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes

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