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osu1110392674.pdf (11.3 MB)
ETD Abstract Container
Abstract Header
Studies toward the enantioselective total synthesis of pectenotoxin 2
Author Info
Bondar, Dmitriy A.
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=osu1110392674
Abstract Details
Year and Degree
2005, Doctor of Philosophy, Ohio State University, Chemistry.
Abstract
Studies toward the enantioselective total synthesis of the marine natural toxin pectenotoxin 2 are described. A successful approach to a fully functionalized precursor to the C(29)-C(40) F/G sector began with the establishment of a proper stereochemical relationship between the hydroxyl and methyl substituents at C(37) and C(38) and involved an anti-aldol reaction. The F ring framework was merged by means of vinyl anion coupling. A new hydroxyl-directed hydrogenation protocol featuring ionic bonding between an alkoxide and rhodium catalyst was invented to arrest the pronounced tendency of hydroxy dihydrofurans to undergo dehydration to form more stable furans. A great level of efficiency was gained by routing the synthesis of the C(16)-C(26) subunit through a common intermediate. The carbon framework was then assembled via a Julia coupling process. The resulting double bond was oxidized by way of a Sharpless asymmetric dihydroxylation reaction to produce two new sterecenters and form the ring E tetrahydrofuranyl system. Access to the C(1)-C(15) building block was achieved by convergent coupling of a lithiated alkane to a Weinreb amide. The spirocyclic A/B motif was next constructed in a synchronous manner by two-fold p-methoxybenzyl ether deprotection. Catalytic á-hydroxylation of a conjugated double bond was called upon to complete the oxygenation pattern of this fragment. Union of the C(1)-C(15) and C(16)-C(26) fragments by means of Julia olefination led to construction of the AB(CD)E eastern hemisphere of pectenotoxin 2. Although the route to this target is far from complete, knowledge collected herein should pave the way toward completion of the total synthesis of this fascinating natural product.
Committee
Leo Paquette (Advisor)
Pages
211 p.
Subject Headings
Chemistry, Organic
Keywords
pectenotoxins synthesis
;
hydroxyl-directed hydrogenation
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Citations
Bondar, D. A. (2005).
Studies toward the enantioselective total synthesis of pectenotoxin 2
[Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1110392674
APA Style (7th edition)
Bondar, Dmitriy.
Studies toward the enantioselective total synthesis of pectenotoxin 2.
2005. Ohio State University, Doctoral dissertation.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=osu1110392674.
MLA Style (8th edition)
Bondar, Dmitriy. "Studies toward the enantioselective total synthesis of pectenotoxin 2." Doctoral dissertation, Ohio State University, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=osu1110392674
Chicago Manual of Style (17th edition)
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Document number:
osu1110392674
Download Count:
865
Copyright Info
© 2005, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.