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Cycloisomerization and Carbocyclization Reactions of Allenes for the Synthesis of Cross-Conjugated Trienes and Tryptophan-Derived Scaffolds

Painter, Thomas Oliver (2009) Cycloisomerization and Carbocyclization Reactions of Allenes for the Synthesis of Cross-Conjugated Trienes and Tryptophan-Derived Scaffolds. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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A strategy for the preparation of 3-vinyl-2-alkylidene-3-cyclohexen-1-ones has been developed using an intramolecular rhodium(I)-catalyzed carbocyclization reaction of allene-ynones. Application of this strategy towards the preparation of analogs of the anticancer agent irofulven was realized, leading to highly functionalized spiro[2.5]octatrienes.A novel approach to ε-lactams from allene-containing propargyl amides has been achieved, also using the rhodium(I)-catalyzed carbocyclization reaction. Further elaboration of this strategy has afforded triene-containing azepines and a pyrroloazepinone.A diverging diversity-oriented synthesis (DOS) strategy using tryptophan as a key starting material was investigated. Constructon of allenic tetrahydro-β-carboline scaffolds via a Pictet-Spengler reaction and subsequent silver(I)-catalyzed cycloisomerization afforded tetrahydroindolizinoindoles. Conversion of the tetrahydro-β-carboline to an allenic propiolamide followed by a microwave-assisted allenic [2 + 2] cycloaddition reaction provided tetrahydrocyclobutaindoloquinolizinones. An allene-yne substituted derivative of tryptophan gave indolylmethylazabicyclooctadiene when subjected to a microwave-assisted allenic [2 + 2] cycloaddition reaction. This same tryptophan-derived precursor afforded an indolylmethyldihydrocyclopentapyridinone when subjected to a rhodium(I)-catalyzed cyclocarbonylation reaction.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Painter, Thomas Olivertopst3@pitt.eduTOPST3
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairBrummond, Kay M.kbrummon@pitt.eduKBRUMMON
Committee MemberCurran, Dennis P.curran@pitt.eduCURRAN
Committee MemberLazo, John S.lazo@pitt.eduLAZO
Committee MemberMeyer, Tara Y.tmeyer@pitt.eduTMEYER
Date: 17 June 2009
Date Type: Completion
Defense Date: 18 March 2009
Approval Date: 17 June 2009
Submission Date: 11 March 2009
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: allene-yne; carbocyclization; cycloaddition; cyclocarbonylation; cycloisomerization; lactams; transition metal
Other ID:, etd-03112009-122213
Date Deposited: 10 Nov 2011 19:32
Last Modified: 15 Nov 2016 13:37


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