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PART I. Transition Metal-Catalyzed Synthesis of Substituted Phenanthrenes PART II. Determination of Double-Bond Positions in Unsaturated Natural Products by Cross-Metathesis
PART I. 전이 금속 촉매 하 치환된 페난트렌 합성 PART II. 교차 복분해 반응을 이용한 불포화 천연물의 이중 결합 위치 결정

DC Field Value Language
dc.contributor.advisor김상희-
dc.contributor.author권용석-
dc.date.accessioned2017-07-13T16:37:44Z-
dc.date.available2017-07-13T16:37:44Z-
dc.date.issued2016-02-
dc.identifier.other000000132672-
dc.identifier.urihttps://hdl.handle.net/10371/120123-
dc.description학위논문 (박사)-- 서울대학교 대학원 : 약학대학 약학과, 2016. 2. 김상희.-
dc.description.abstractPART I. Transition Metal-Catalyzed Synthesis of Substituted Phenanthrenes

Yongseok Kwon
Pharmaceutical Chemistry Major
College of Pharmacy
Graduate School of Seoul National University

Phenanthrenes are important structural motifs in medicinal chemistry and materials science. A number of synthetic strategies have been developed for the construction of the phenanthrene skeleton. Among these approaches, transition metal-catalyzed cycloisomerization of o-alkynylbiaryls has attracted much attention because it has the potential to allow efficient access to extensive structural variations. However, this strategy necessarily possesses regioselectivity problems
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dc.description.abstract6-endo-dig vs 5-exo-dig depending on the metal catalyst and the substituents on the alkyne terminus.
Therefore, transition metal-catalyzed cyclizations of o-propargylbiaryls and biaryl propargyl alcohols have been developed to provide an alternative and selective path for the synthesis of highly substituted phenanthrenes. A catalytic amount of indium salt (III) induced the hydroarylation of o-propargylbiaryls and subsequent exo-endo double bond isomerization to afford substituted phenanthrenes. The cyclization of biaryl propargyl alcohols effectively proceeds in the presence of platinum salt to construct phenanthrene skeletons with carbene functionality. The complete regioselectivity of both cyclization processes for six over seven membered rings has been achieved.

PART II. Determination of Double-Bond Positions in Unsaturated Natural Products by Cross-Metathesis

Yongseok Kwon
Pharmaceutical Chemistry Major
College of Pharmacy
Graduate School of Seoul National University

Accurate identification of the double bond positions in long-chain olefins remains a challenge. The current analytical approaches for solving this problem depend on the use of mass spectrometry (MS). Conventional MS is inherently unreliable primarily due to rapid isomerization of the molecular ions. One solution to this problem involves the prior chemical derivatization of the analyte. This method has been commonly used by laboratories that do not specialize in MS. However, this approach suffers from several drawbacks including the need for a second derivatization step and possible interference from other functional groups on the analyte during derivatization.
Therefore, a new chemical derivatization method for the determination of the double-bond positions in long-chain olefins has been developed. This method is based on a cross-metathesis (CM) reaction between the target compound and a simple olefin. Depending on the CM partner used, the resulting fragments possess distinctive physicochemical properties that are appropriate for LC/MS and GC/MS analysis. The position of the double bond can be deduced simply by comparing the changes in molecular mass. Both of the presented methods for LC/MS and GC/MS are equally reliable and applicable at a sub-milligram scale.
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dc.description.tableofcontentsPART I. Transition Metal-Catalyzed Synthesis of Substituted Phenanthrenes 1
I. Introduction 2
1. Cycloisomerization of o-Propargylbiaryls 2
2. Cyclization of Biaryl Propargyl Alcohols 5
II. Results and Discussion 8
1. Cycloisomerization of o-Propargylbiaryls 8
2. Cyclization of Biaryl Propargyl Alcohols 14
III. Conclusion 23
IV. Experimental Section 24
1. Cycloisomerization of o-Propargylbiaryls 25
1.1. Preparation of the Starting Materials 24
1.2. Cycloisomerization of o-Propargylbiaryls 44
2. Cyclization of Biaryl Propargyl Alcohols 55
2.1. Preparation of the Starting Materials 55
2.2. Cyclization of Biaryl Propargyl Alcohols 75
2.3. Total Synthesis of Antofine 90
V. References 98

PART II. Determination of Double-Bond Positions in Unsaturated Natural Products by Cross-Metathesis 104
I. Introduction 105
II. Results and Discussion 109
III. Conclusion 119
IV. Experimental Section 120
1. Synthesis of CM Products 6 and 7 121
2. Analytical Methods for LC/MS and GC/MS 123
V. References 124

Appendix A 126
Appendix B 213
Appendix C 216

Abstract in Korean 239
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dc.formatapplication/pdf-
dc.format.extent17251800 bytes-
dc.format.mediumapplication/pdf-
dc.language.isoen-
dc.publisher서울대학교 대학원-
dc.subject6-exo-dig-
dc.subjectbiaryl propargyl alcohol-
dc.subjectcyclization-
dc.subjecto-propargylbiaryl-
dc.subjectphenanthrene-
dc.subjecttransition metal-
dc.subjectdouble bonds-
dc.subjectfatty acids-
dc.subjectmetathesis-
dc.subjectolefins-
dc.subjectstructure elucidation-
dc.subject.ddc615-
dc.titlePART I. Transition Metal-Catalyzed Synthesis of Substituted Phenanthrenes PART II. Determination of Double-Bond Positions in Unsaturated Natural Products by Cross-Metathesis-
dc.title.alternativePART I. 전이 금속 촉매 하 치환된 페난트렌 합성 PART II. 교차 복분해 반응을 이용한 불포화 천연물의 이중 결합 위치 결정-
dc.typeThesis-
dc.description.degreeDoctor-
dc.citation.pages236-
dc.contributor.affiliation약학대학 약학과-
dc.date.awarded2016-02-
Appears in Collections:
College of Pharmacy (약학대학)Dept. of Pharmacy (약학과)Theses (Ph.D. / Sc.D._약학과)
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