Link to the University of Pittsburgh Homepage
Link to the University Library System Homepage Link to the Contact Us Form

Development and Synthesis Applications of Olefin Isomerization-Claisen Rearrangement Reactions

Wang, Kan (2008) Development and Synthesis Applications of Olefin Isomerization-Claisen Rearrangement Reactions. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

Primary Text

Download (1MB) | Preview


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.


Social Networking:
Share |


Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Wang, Kankaw87@pitt.eduKAW87
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairNelson, Scott Gsgnelson@pitt.eduSGNELSON
Committee MemberDay, Billybday@pitt.eduBDAY
Committee MemberWilcox, Craigdaylite@pitt.eduDAYLITE
Committee MemberCohen, Theodorecohen@pitt.eduCOHEN
Date: 29 January 2008
Date Type: Completion
Defense Date: 29 November 2007
Approval Date: 29 January 2008
Submission Date: 20 December 2006
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: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Olefin Isomerization-Claisen Rearrangement Reactio
Other ID:, etd-12202006-173358
Date Deposited: 10 Nov 2011 20:11
Last Modified: 15 Nov 2016 13:54


Monthly Views for the past 3 years

Plum Analytics

Actions (login required)

View Item View Item