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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. (Unpublished)

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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
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Penich, Jessie Michaeljmp135@pitt.eduJMP135
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairNelson, Scott Gsgnelson@pitt.eduSGNELSON
Committee MemberBrummond, Kay Mkbrummon@pitt.eduKBRUMMON
Committee MemberHorne, Sethhorne@pitt.eduHORNE
Date: 14 September 2011
Date Type: Completion
Defense Date: 6 May 2011
Approval Date: 14 September 2011
Submission Date: 19 May 2011
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: catalysis; Claisen Rearrangement; organic chemistry; transition metal; aldehyde; allylic substitution; picolinamide; metal-allyl
Other ID: http://etd.library.pitt.edu/ETD/available/etd-05192011-203620/, etd-05192011-203620
Date Deposited: 10 Nov 2011 19:45
Last Modified: 15 Nov 2016 13:43
URI: http://d-scholarship.pitt.edu/id/eprint/7918

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