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Studies toward the total synthesis of salicylihalamide A Chandler, Melanie K.
Abstract
This thesis describes studies toward the synthesis of enamide macrolide salicylihalamide A (1). The convergent synthetic plan requires assembly of three main subunits whose eventual coupling should provide salicylihalamide A. Construction of two key fragments encompassing the sensitive (Z, Z)-diene sidechain (177) and the functionalized aromatic portion (142) of the target 1 have been realized, Compound 142 was efficiently synthesized using the accelerative effects of CuCI on the Pd(0)-catalyzed Stille coupling between o-substituted aromatic triflate 140 and allyl tributylstannane. The diene 177 was generated using a copper(l) thiophenecarboxylate mediated cross-coupling between vinyl stannane 181 and iodide 180. The reaction was stereospecific, rapid and mild enough to allow efficient construction of this hindered and labile sidechain. Preliminary investigations into the enantioselective synthesis of the remaining subunit culminated in the formation of aldehyde 95. During the course of this work a new protocol for generating Z-vinyl stannanes such as 181 from (trimethylsilyl)acetylene was also developed.
Item Metadata
Title |
Studies toward the total synthesis of salicylihalamide A
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
2001
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Description |
This thesis describes studies toward the synthesis of enamide macrolide
salicylihalamide A (1). The convergent synthetic plan requires assembly of three main
subunits whose eventual coupling should provide salicylihalamide A.
Construction of two key fragments encompassing the sensitive (Z, Z)-diene
sidechain (177) and the functionalized aromatic portion (142) of the target 1 have been
realized, Compound 142 was efficiently synthesized using the accelerative effects of
CuCI on the Pd(0)-catalyzed Stille coupling between o-substituted aromatic triflate 140
and allyl tributylstannane. The diene 177 was generated using a copper(l)
thiophenecarboxylate mediated cross-coupling between vinyl stannane 181 and iodide
180. The reaction was stereospecific, rapid and mild enough to allow efficient
construction of this hindered and labile sidechain. Preliminary investigations into the
enantioselective synthesis of the remaining subunit culminated in the formation of
aldehyde 95.
During the course of this work a new protocol for generating Z-vinyl stannanes
such as 181 from (trimethylsilyl)acetylene was also developed.
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Extent |
3551027 bytes
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Genre | |
Type | |
File Format |
application/pdf
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Language |
eng
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Date Available |
2009-08-04
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Provider |
Vancouver : University of British Columbia Library
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Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
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DOI |
10.14288/1.0061482
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
2001-11
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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Item Media
Item Citations and Data
Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.