eprintid: 19931
rev_number: 8
userid: 2559
dir: disk0/00/01/99/31
datestamp: 2014-01-31 20:56:00
lastmod: 2016-11-15 14:15:37
status_changed: 2014-01-31 20:56:00
type: thesis_degree
metadata_visibility: show
contact_email: lianglcl@gmail.com
item_issues_count: 0
eprint_status: archive
creators_name: Lu, Chunliang
creators_email: chl110@pitt.edu
creators_id: CHL110
title: Stereoselective Synthesis of Spirooxindole Amides and Cyanohydrin Alkyl Ethers
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: Hydrozirconation, Spirooxindole Amides, Hydrocyanation, Asymmetric Catalysis,Cyanohydrin Alkyl Ethers
abstract: A new family of spirooxindole amides were synthesized by a sequence of hydrozirconation, acylation, and intramolecular cyclization reactions. Three of the four possible diastereomers can be obtained as the major isomers through this process. The spirooxindole structure has many points for diversification, and a 37-membered library was synthesized through this approach by collaborators. A comparison with known compound collections showed that this new spirooxindole library possessed good chemical diversity.

Cyanohydrin alkyl ethers, the key intermediate in the above multi-component hydrozironation reaction, were effectively synthesized through a Brønsted acid-mediated hydrocyanation of vinyl ethers. The enantiomerically enriched product can be obtained by asymmetric hydrocyanation of vinyl ethers catalyzed by a chiral Brønsted acid, and the catalyst
can be regenerated by PhOH. As far as we know, this research represents the first example of chiral Brønsted acid mediated intermolecular addition of silylated nucleophiles with vinyl ethers. The ion pair interaction between the conjugate base of the chiral Brønsted acid and the
oxocarbenium ion was revealed by computational modeling, which explained the origin of the enantioselectivity and the substrate scope of this reaction.
date: 2014-01-31
date_type: published
pages: 150
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Floreancig, Paul
etdcommittee_name: Brummond, Kay
etdcommittee_name: Cohen, Theodore
etdcommittee_name: Xie, Xiang-Qun
etdcommittee_email: florean@pitt.edu
etdcommittee_email: kbrummon@pitt.edu
etdcommittee_email: cohen@pitt.edu
etdcommittee_email: xix15@pitt.edu
etdcommittee_id: FLOREAN
etdcommittee_id: KBRUMMON
etdcommittee_id: COHEN
etdcommittee_id: XIX15
etd_defense_date: 2013-10-01
etd_approval_date: 2014-01-31
etd_submission_date: 2013-10-23
etd_release_date: 2014-01-31
etd_access_restriction: immediate
etd_patent_pending: FALSE
thesis_type: dissertation
degree: PhD
citation:   Lu, Chunliang  (2014) Stereoselective Synthesis of Spirooxindole Amides and Cyanohydrin Alkyl Ethers.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/19931/1/Dissertation_Chunliang_Lu_revised_oct-23.pdf