eprintid: 26163
rev_number: 58
userid: 2413
dir: disk0/00/02/61/63
datestamp: 2016-10-03 21:00:50
lastmod: 2016-11-15 14:30:26
status_changed: 2016-10-03 21:00:50
type: thesis_degree
metadata_visibility: show
contact_email: dlyyzz@gmail.com
item_issues_count: 0
eprint_status: archive
creators_name: Yan, Yongzhao
creators_email: yoy11@pitt.edu
creators_id: YOY11
title: ENANTIOSELECTIVE SYNTHESIS AND CYCLOISOMERIZATION OF 1-BICYCLO[1.1.0]BUTAN-1-YL ALKYLAMINES
ispublished: unpub
divisions: sch_as_chemistry
full_text_status: public
keywords: Cycloisomerization, Bicyclo[1.1.0]butane, Palladium, Synthetic Method,
abstract: This dissertation demonstrates the synthesis and application studies of 1-bicyclo[1.1.0]butyl alkylamines. The enantioselective synthesis of 1-bicyclo[1.1.0]butyl alkylamines was achieved by dicarbene addition to enantiomerically enriched propargyl amides. The enantioselective addition of alkynes to imines proceeded well for most N-DPP amides. But the carbene addition suffered from the formation of cyclopropane byproducts. However, a series of silyl-substituted bicyclo[1.1.0]butanes could be synthesized by this methodology in high, reproducible yields. When tethered to an activated alkyne, the silyl-substituted bicyclo[1.1.0]butane undergoes cyclization to form pyrrolidines. 
In the application of the 1-bicyclo[1.1.0]butyl alkylamines, a palladium(0)-catalyzed cycloisomerization of bicyclo[1.1.0]butanes and methylenecyclopropanes has been developed. 3-Azaspiro[bicyclo[3.1.0] hexane-6,1'-cyclopropane] is obtained with excellent stereoselectivity. Novel 2,3,3a,6a- tetrahydrocyclopenta[c]pyrrol-4(1H)-one is the product of the cycloisomerization and carbonylation sequence.
date: 2016-10-03
date_type: published
pages: 203
institution: University of Pittsburgh
refereed: TRUE
etdcommittee_type: committee_chair
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_type: committee_member
etdcommittee_name: Wipf, Peter
etdcommittee_name: Curran, Dennis P
etdcommittee_name: Horne, Seth W
etdcommittee_name: Tidgewell, Kevin
etdcommittee_email: pwipf@pitt.edu
etdcommittee_email: curran@pitt.edu
etdcommittee_email: horne@pitt.edu
etdcommittee_email: tidgewellk@duq.edu
etdcommittee_id: PWIPF
etdcommittee_id: CURRAN
etdcommittee_id: HORNE
etdcommittee_id: 
etd_defense_date: 2016-05-19
etd_approval_date: 2016-10-03
etd_submission_date: 2015-10-07
etd_release_date: 2016-10-03
etd_access_restriction: immediate
etd_patent_pending: FALSE
thesis_type: dissertation
degree: PhD
citation:   Yan, Yongzhao  (2016) ENANTIOSELECTIVE SYNTHESIS AND CYCLOISOMERIZATION OF 1-BICYCLO[1.1.0]BUTAN-1-YL ALKYLAMINES.  Doctoral Dissertation, University of Pittsburgh.    (Unpublished)  
document_url: http://d-scholarship-dev.library.pitt.edu/26163/4/Thesis_Yongzhao_Yan_2016.6.25.pdf