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

RHODIUM(I)-CATALYZED CYCLOISOMERIZATION OF NITROGEN TETHERED ENE-ALLENES: FORMATION OF TETRAHYDROAZEPINES

Casarez, Anthony David (2005) RHODIUM(I)-CATALYZED CYCLOISOMERIZATION OF NITROGEN TETHERED ENE-ALLENES: FORMATION OF TETRAHYDROAZEPINES. Master's Thesis, University of Pittsburgh. (Unpublished)

[img]
Preview
PDF
Primary Text

Download (9MB) | Preview

Abstract

Abstract: A novel cycloisomerization process involving nitrogen-tethered 1,6-ene-allenes has been realized. Subjecting ene-allene 9 to rhodium biscarbonyl chloride dimer produces tetrahydroazepine 10 in moderate to high yields. Substituting the allene moiety with the bulky tert-butyl-group (R4 = t-Bu), while employing a trans-alkene tether, afforded the corresponding azepines in the highest yields. This formal Alder-ene transformation tolerated not only a variety of alkyl-substituents on both the alkene and allene portions but also silyl-[R2 = SiMe3, SiMe2Bn; R4 = Si(i-Pr)3] and phenyl-(R2 = Ph, R4 = Ph) substituents. A deuterium labeling study aided in the postulation of two possible mechanisms for this cycloisomerization. During the course of this investigation, a novel carbon monoxide insertion reaction was observed. Our findings to date are reported and discussed herein.


Share

Citation/Export:
Social Networking:
Share |

Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Casarez, Anthony Davidadc9@pitt.eduADC9
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairBrummond, Kay Mkbrummon@pitt.eduKBRUMMON
Committee MemberCurran, Dennis Pcurran@pitt.eduCURRAN
Committee MemberFloreancig, Paul Eflorean@pitt.eduFLOREAN
Date: 7 June 2005
Date Type: Completion
Defense Date: 24 November 2004
Approval Date: 7 June 2005
Submission Date: 15 April 2005
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: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: azepine; cycloisomerization; ene-allenes; rhodium
Other ID: http://etd.library.pitt.edu/ETD/available/etd-04152005-164304/, etd-04152005-164304
Date Deposited: 10 Nov 2011 19:37
Last Modified: 15 Nov 2016 13:40
URI: http://d-scholarship.pitt.edu/id/eprint/7190

Metrics

Monthly Views for the past 3 years

Plum Analytics


Actions (login required)

View Item View Item