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Dissertation Information for Svetlana Burova

NAME:
- Svetlana Burova

DEGREE:
- Ph.D.

DISCIPLINE:
- Chemistry

SCHOOL:
- Emory University (USA) (2003)

ADVISORS:
- Frank E. McDonald

COMMITTEE MEMBERS:
- Dennis C. Liotta
- Lanny S. Liebeskind

MPACT Status: Fully Complete

Title: Part I. Sulfur- alkyne cyclization for formation of dihydrothiophenes and annulated thiophenols. Part II. Six-carbon modular approach to polyacetate synthesis. Total synthesis of polyene macrolide RK-397

Abstract: Part I. Cycloisomerization of homopropargylic thiols to dihydrothiophenes is promoted by group VI metal carbonyls. Related thiacyclizations under basic and radical conditions were also studied, including regioselective formation of benzothiophenes from aryl methyl sulfides and alkynes. This methodology was utilized in a short and regioselective formal synthesis of raloxifene, a selective estrogen receptor modulator, and a drug for treatment of postmenopausai osteoporosis. Part II. Total Synthesis of Polyene Macrolide RK-397. A new synthetic strategy for assembling polyacetate substructures has been developed and is based on the efficient coupling of functionalized nucleophilic alkynyl modules 1 with electrophilic six-carbon epoxy alkynyl modules 2 .Hydration of the internal alkyne in the coupled products and stereoselective reduction of the resulting ketone intermediate provides a general approach to a library of stereoisomeric 1, 3, 5,...alternating polyols 3 . The strategy was initially demonstrated in a stereoselective synthesis of the C11-C28 polyol substructure of the natural product RK-397. Utilizing our previously developed methodology for polyacetate construction the first total synthesis of polyene macrolide RK-397 was completed, confirming the stereochemical assignment. Key characteristics of the RK-397 synthesis include olefin cross-metathesis for C28-C29 bond, nucleophilic epoxide opening with alkynyl nucleophiles, intramolecular hydrosilylation-oxidation of intermediate homopropargylic alcohols for introduction of รข-hydroxyketone functionality and Stille approach to polyene introduction. Highly convergent nature of our synthetic approach should be valuable for synthesis of other members of the polyene macrolide class and of RK-397 analogs.

MPACT Scores for Svetlana Burova

A = 0
C = 0
A+C = 0
T = 0
G = 0
W = 0
TD = 0
TA = 0
calculated 2008-03-23 20:38:58

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