Link to the University of Pittsburgh Homepage
Link to the University Library System Homepage Link to the Contact Us Form

I. LEWIS BASE-CATALYZED ALDOL REACTION IN THE TOTAL SYNTHESIS OF ERYTHRONOLIDE B; II. EFFORTS TOWARDS THE TOTAL SYNTHESIS OF AMPHIDINOLIDE H

Fu, Dezhi (2011) I. LEWIS BASE-CATALYZED ALDOL REACTION IN THE TOTAL SYNTHESIS OF ERYTHRONOLIDE B; II. EFFORTS TOWARDS THE TOTAL SYNTHESIS OF AMPHIDINOLIDE H. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

[img]
Preview
PDF
Primary Text

Download (1MB) | Preview

Abstract

Lewis base (trimethylsilylquinine and trimethylsilylquinidine) catalyzed acyl halide-aldehyde cyclocondensation (AAC) reactions have been developed to prepare synthetically important bispropionate units previously by the Nelson group. A new Lewis base-catalyzed diastereoselective Mukaiyama aldol reaction has extended this bispropionate unit preparation methodology to all-syn bispropionates which widely occurred in polypropionate natural products. By using phenoxides as Lewis base catalysts, enol silanes were activated and underwent a Felkin attack on an aldehyde through an antiperiplanar transition state to generate all-syn bispropionate product in high yields and excellent diastereoselectivities.All-syn bispropionate prepared from the Lewis base-catalyzed diastereoselective Mukaiyama aldol reaction has been untilized in natural product synthesis of erythronolide B establishing ¡°syn,syn,syn¡± stereochemical relationships from C2-C5.Studies towards the total synthesis of the cytotoxic marine macrolide amphidinolide H have been disclosed. By exploiting AAC methodology, several key stereochemical relationships present in major fragments 198 and 199 were established. A highly enantioselective synthesis of methyl ketone 200 was realized from commercially available (S)-(−)-glycidol. Iodide 198 was coupled with boronic ester 199 via an efficient Suzuki reaction to form a C7-C20 fragment.


Share

Citation/Export:
Social Networking:
Share |

Details

Item Type: University of Pittsburgh ETD
Status: Unpublished
Creators/Authors:
CreatorsEmailPitt UsernameORCID
Fu, Dezhifudezhi147@gmail.comfudezhi147@gmail.com
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairNelson, Scott Gsgnelson@pitt.edusgnelson@pitt.edu
Committee MemberDay, Billy Wbday@pitt.edubday@pitt.edu
Committee MemberWilcox, Craig Sdaylite@pitt.edudaylite@pitt.edu
Committee MemberCohen, Theodorecohen@pitt.educohen@pitt.edu
Date: 22 June 2011
Date Type: Completion
Defense Date: 8 April 2011
Approval Date: 22 June 2011
Submission Date: 15 April 2011
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: AAC; Amphidinolide H; Erythronolide B; Lewis Base; Macrolides; Mukaiyama Aldol; Ployketide
Other ID: http://etd.library.pitt.edu/ETD/available/etd-04152011-183517/, etd-04152011-183517
Date Deposited: 10 Nov 2011 19:37
Last Modified: 08 May 2012 13:30
URI: http://d-scholarship.pitt.edu/id/eprint/7211

Metrics

Monthly Views for the past 3 years

Plum Analytics


Actions (login required)

View Item View Item