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Ruthenium-Catalyzed [3,3]-Sigmatropic Rearrangements of α-Branched Allyl Vinyl Ethers

Penich, Jessie Michael (2011) Ruthenium-Catalyzed [3,3]-Sigmatropic Rearrangements of α-Branched Allyl Vinyl Ethers. Master's Thesis, University of Pittsburgh.

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    Abstract

    Previous research carried out in our group has demonstrated the ability of the cationic ruthenium complex [CpRu(MeCN)3]PF6 in tandem with a chiral picolinamide ligand and a Lewis acid co-catalyst to facilitate the catalytic, asymmetric [3,3]-sigmatropic rearrangement of α-unbranched aromatic allyl vinyl ethers at ambient temperature. This thesis describes my efforts to a.) extend the Ru-catalyzed Claisen methodology to α-branched substrates and b.) investigate the mechanism of this class of transformation. It was determined that [CpRu(MeCN)3]PF6 in conjunction with several novel N-phenol picolinomide ligands serve as highly-active catalysts for the rearrangement of α-branched aromatic allyl vinyl ethers. Although regio- and stereoselectivity are poor at this point, reactions proceed to complete conversion at ambient temperature in as little as 2 h in CH2Cl2 with no Lewis acid or any other additives required.

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    Details

    Item Type: University of Pittsburgh ETD
    ETD Committee:
    ETD Committee TypeCommittee MemberEmail
    Committee ChairNelson, Scott Gsgnelson@pitt.edu
    Committee MemberBrummond, Kay Mkbrummon@pitt.edu
    Committee MemberHorne, Sethhorne@pitt.edu
    Title: Ruthenium-Catalyzed [3,3]-Sigmatropic Rearrangements of α-Branched Allyl Vinyl Ethers
    Status: Unpublished
    Abstract: Previous research carried out in our group has demonstrated the ability of the cationic ruthenium complex [CpRu(MeCN)3]PF6 in tandem with a chiral picolinamide ligand and a Lewis acid co-catalyst to facilitate the catalytic, asymmetric [3,3]-sigmatropic rearrangement of α-unbranched aromatic allyl vinyl ethers at ambient temperature. This thesis describes my efforts to a.) extend the Ru-catalyzed Claisen methodology to α-branched substrates and b.) investigate the mechanism of this class of transformation. It was determined that [CpRu(MeCN)3]PF6 in conjunction with several novel N-phenol picolinomide ligands serve as highly-active catalysts for the rearrangement of α-branched aromatic allyl vinyl ethers. Although regio- and stereoselectivity are poor at this point, reactions proceed to complete conversion at ambient temperature in as little as 2 h in CH2Cl2 with no Lewis acid or any other additives required.
    Date: 14 September 2011
    Date Type: Completion
    Defense Date: 06 May 2011
    Approval Date: 14 September 2011
    Submission Date: 19 May 2011
    Access Restriction: No restriction; Release the ETD for access worldwide immediately.
    Patent pending: No
    Institution: University of Pittsburgh
    Thesis Type: Master's Thesis
    Refereed: Yes
    Degree: MS - Master of Science
    URN: etd-05192011-203620
    Uncontrolled Keywords: catalysis; Claisen Rearrangement; organic chemistry; transition metal; aldehyde; allylic substitution; picolinamide; metal-allyl
    Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
    Date Deposited: 10 Nov 2011 14:45
    Last Modified: 12 Jun 2012 16:11
    Other ID: http://etd.library.pitt.edu/ETD/available/etd-05192011-203620/, etd-05192011-203620

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