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dc.contributor.authorBian, Zhiguoen_US
dc.date.accessioned2014-07-22T18:47:55Z
dc.date.available2014-07-22T18:47:55Z
dc.date.created2010en_US
dc.date.issued2010en_US
dc.identifieretd-04262010-122911en_US
dc.identifierumi-10124en_US
dc.identifiercat-001531611en_US
dc.identifier.urihttps://repository.tcu.edu:443/handle/116099117/4209
dc.descriptionTitle from dissertation title page (viewed May 20, 2010).en_US
dc.descriptionIncludes abstract.en_US
dc.descriptionThesis (Ph.D.)--Texas Christian University, 2010.en_US
dc.descriptionDepartment of Chemistry; advisor, David E. Minter.en_US
dc.descriptionIncludes bibliographical references.en_US
dc.descriptionText (electronic thesis) in PDF.en_US
dc.description.abstractThe crinine-type alkaloids, which have the 5,10b-ethanophenanthridine skeleton as the core structure, represent an important sub-class of the family of Amaryllidaceae alkaloids. Considering the obvious structural relationship between the crinine-type alkaloids and the isoquinoline nucleus, a synthetic strategy involving the construction of the crinane skeleton from isoquinoline would be a logical approach. In order to realize this goal, a novel methodology to prepare 4,4-disubstituted 1,4-dihydroisoquinolines through boron-activated enamine chemistry has been developed in our lab. This method provides not only a quaternary carbon center at C-4 but also an imine group that can be further functionalized. A systemic investigation of the reductive alkylation of isoquinoline using boron-activated enamine chemistry was performed in order to examine the scope of this methodology for preparing 4,4-disubstituted isoquinoline derivatives. Various functional groups including simple alkyls, allyl, protected alcohols, protected aldehydes, and esters were successfully introduced at C-4 of the 1,4-dihydroisoquinoline product. Additionally, several spiro compounds and imines with two different substituents at C-4 were also synthesized. Based on this method, (?)-crinine was efficiently prepared in 9 steps in 14.4% overall yield for the first time from 6,7-methylenedioxyisoquinoline using an AB-->D-->C sequence. This method was then applied to build the skeletons of delagoenine and delagoensine - two very unusual alkaloids possessing a hemiaminal function in the D-ring.en_US
dc.format.mediumFormat: Onlineen_US
dc.language.isoengen_US
dc.publisher[Fort Worth, Tex.] : Texas Christian University,en_US
dc.relation.ispartofTexas Christian University dissertationen_US
dc.relation.ispartofUMI thesis.en_US
dc.relation.ispartofTexas Christian University dissertation.en_US
dc.relation.requiresMode of access: World Wide Web.en_US
dc.relation.requiresSystem requirements: Adobe Acrobat reader.en_US
dc.subject.lcshAlkaloids.en_US
dc.subject.lcshIsoquinoline.en_US
dc.subject.lcshOrganic compounds Synthesis.en_US
dc.titleSynthetic approaches to the skeleton of crinine-type alkaloids from isoquinoline and the total synthesis of (?)-crinine [electronic resource] /en_US
dc.typeTexten_US
etd.degree.departmentDepartment of Chemistry
etd.degree.levelDoctoral
local.academicunitDepartment of Chemistry and Biochemistry
local.subjectareaChemistry and Biochemistry


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