Copyright
by
David Earl Kaelin Jr.
2002
The Dissertation Committee for David Earl Kaelin Jr.
certifies that this is the approved version of the following dissertation:
Novel Methodologies for the Synthesis of C-Aryl Glycosides and
Progress Toward the Synthesis of the C-Aryl Glycoside Natural
Products Galtamycinone and Kidamycin
Committee:
_______________________________
Stephen F. Martin, Supervisor
_______________________________
Philip D. Magnus
_______________________________
Nathan L. Bauld
_______________________________
Marvin L. Hackert
_______________________________
Christian P. Whitman
Novel Methodologies for the Synthesis of C-Aryl Glycosides and
Progress Toward the Synthesis of the C-Aryl Glycoside Natural
Products Galtamycinone and Kidamycin
by
David Earl Kaelin Jr., B.S.
Dissertation
Presented to the Faculty of the Graduate School of
The University of Texas at Austin
in Partial Fulfillment
of the Requirements
for the Degree of
Doctor of Philosophy
The University of Texas at Austin
December, 2002
iv
Novel Methodologies for the Synthesis of C-Aryl Glycosides and
Progress Toward the Synthesis of the C-Aryl Glycoside Natural
Products Galtamycinone and Kidamycin
Publication No. _________
David Earl Kaelin Jr., Ph.D.
The University of Texas at Austin, 2002
Supervisor: Stephen F. Martin
The development of methodologies for the synthesis of C-aryl glycosides has
been described. Novel C-aryl glycosides were prepared by [4+2] cycloadditions
between benzynes and glycosyl-substituted furans. A modification of the cycloaddition
approach, wherein the two reactants were linked via a cleavable tether, allowed C-aryl
glycosides to be prepared in a highly regioselective manner. An alternate method for the
preparation of C-aryl glycosides via an SN2' ring opening reaction of benzyne/furan
cycloadducts with sugar nucleophiles has been described.
Extension of the benzyne/glycosyl-substituted furan cycloaddition methodology
to natural product synthesis has been described. A formal total synthesis of the
antitumor ant