eprintid: 10439
rev_number: 4
userid: 6
dir: disk0/00/01/04/39
datestamp: 2011-11-10 20:11:37
lastmod: 2016-11-15 13:54:56
status_changed: 2011-11-10 20:11:37
type: thesis_degree
metadata_visibility: show
contact_email: kaw87@pitt.edu
item_issues_count: 0
eprint_status: archive
creators_name: Wang, Kan
creators_email: kaw87@pitt.edu
creators_id: KAW87
title: Development and Synthesis Applications of Olefin Isomerization-Claisen Rearrangement Reactions
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: Olefin Isomerization-Claisen Rearrangement Reactio
abstract: Iridium(I)-catalyzed olefin isomerization in bis(allyl) ethers is integrated into a generally applicable strategy for affecting highly stereoselective Claisen rearrangements. Catalyzed alkene isomerization affords allyl vinyl ethers from easily prepared di(allyl) ethers; direct thermolysis of these reaction mixtures leads to highly diastereoselective [3,3] sigmatropic rearrangements affording syn-2,3-dialkyl-4-pentenal derivatives. An easily executed strategy for realizing asymmetric variants of the isomerization-Claisen rearrangement (ICR) reactions is also described.Merging the catalytic asymmetric synthesis of di(allyl) ethers with ensuing olefin isomerization-Claisen rearrangement (ICR) reactions provides a convenient, two-step route to asymmetric aliphatic Claisen rearrangements from easily obtained starting materials. These reactions deliver the 2,3-disubstituted 4-pentenal derivatives characteristic of aliphatic Claisen rearrangements with excellent relative and absolute stereocontrol. A catalytic enantioselective synthesis of the (+)-calopin dimethyl ether demonstrates the utility of this reaction technology in asymmetric synthesis enterprises.Stereoselective quaternary all-carbon stereocenter construction is often not easily achieved from methodologies developed primarily for accessing less substituted stereogenic carbons. Olefin isomerization-Claisen rearrangement (ICR) reactions offer a strategy for recruiting the venerable Claisen rearrangement for asymmetric quaternary carbon construction. Several complementary strategies for enantioselective quaternary carbon synthesis derive directly from the ICR reaction design.
date: 2008-01-29
date_type: completed
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Nelson, Scott G
etdcommittee_name: Day, Billy
etdcommittee_name: Wilcox, Craig
etdcommittee_name: Cohen, Theodore
etdcommittee_email: sgnelson@pitt.edu
etdcommittee_email: bday@pitt.edu
etdcommittee_email: daylite@pitt.edu
etdcommittee_email: cohen@pitt.edu
etdcommittee_id: SGNELSON
etdcommittee_id: BDAY
etdcommittee_id: DAYLITE
etdcommittee_id: COHEN
etd_defense_date: 2007-11-29
etd_approval_date: 2008-01-29
etd_submission_date: 2006-12-20
etd_access_restriction: immediate
etd_patent_pending: FALSE
assigned_doi: doi:10.5195/pitt.etd.2011.10439
thesis_type: dissertation
degree: PhD
committee: Scott G. Nelson (sgnelson@pitt.edu) - Committee Chair
committee: Billy Day (bday@pitt.edu) - Committee Member
committee: Craig Wilcox (daylite@pitt.edu) - Committee Member
committee: Theodore Cohen (cohen@pitt.edu) - Committee Member
etdurn: etd-12202006-173358
other_id: http://etd.library.pitt.edu/ETD/available/etd-12202006-173358/
other_id: etd-12202006-173358
citation:   Wang, Kan  (2008) Development and Synthesis Applications of Olefin Isomerization-Claisen Rearrangement Reactions.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/10439/1/wangkanfinal2_etd.pdf