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Catalytic Asymmetric Claisen Rearrangements. The Development of Ru(II)-Catalyzed Formal [3,3] Sigmatropic Rearrangements and Related Enolate Allylation Reactions

Geherty, Maryll / E. (2013) Catalytic Asymmetric Claisen Rearrangements. The Development of Ru(II)-Catalyzed Formal [3,3] Sigmatropic Rearrangements and Related Enolate Allylation Reactions. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Abstract

The Claisen rearrangement, a [3,3] sigmatropic rearrangement, remains an important method for the construction of C-C bonds nearly a century after its discovery. However, methods to affect a catalytic and asymmetric variant of this reaction are rare. A transition metal/Lewis acid co-catalyst system (Ru(II)-B(III)) has been successfully employed to affect an enantioselective, and diastereoselective Claisen rearrangement of simple, achiral, allyl vinyl ethers without the need for auxiliary functionality to assist in substrate-catalyst association. In addition, we have developed a complementary ruthenium catalyzed enolate allylic alkylation reaction that forms Claisen-like products, without the need to synthesize allyl vinyl ethers.

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Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Geherty, Maryll / E.meg60@pitt.eduMEG60
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairNelson, Scott G.sgnelson@pitt.eduSGNELSON
Committee MemberCurran, Dennis Pcurran@pitt.eduCURRAN
Committee MemberWilcox, Craigdaylite@pitt.eduDAYLITE
Committee MemberZhang, Linzhanglx@upmc.eduLIZ22
Date: 25 January 2013
Date Type: Publication
Defense Date: 5 December 2012
Approval Date: 25 January 2013
Submission Date: 29 November 2012
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 172
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Asymmetric Catalysis Claisen Rearrangement [3,3] sigmatropic rearrangement Ruthenium(II) catalysis Vicinal stereocenters Enolate Allylations silyl enolate nucleophiles allyl vinyl ethers Ruthenium(IV)pi-allyl complex
Date Deposited: 25 Jan 2013 19:27
Last Modified: 19 Dec 2016 14:40
URI: http://d-scholarship.pitt.edu/id/eprint/16662

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