General aspects of proposed synthesis of Medium and Macrocyclic Compounds: An important challenge to synthetic chemists is the construction of medium and macrocyclic ring systems. Proposed in Part 1 of this application is our envisioned contribution using what is termed """"""""Boron Template Synthesis"""""""". It is proposed to: (A) Assess the synthetic potential of forming bicyclic carboranes via hydroboration/carbonylation or equivalent process of heteroatom substituted triene substrates. (B) This boracycle will then be treated under conditions that effect fragmentation (Grob) to yield olefinic heterocycles containing a medium size ring (boron = heteroatom). Finally (C), the properties and synthetic utility, through replacement of Boron, of these boracycles will be investigated. Sesquiterpene (Pacifigorgo1) Total Synthesis: A Look at the Stereochemistry of Riveting. An important advantage in using the """"""""Boron Template"""""""" synthetic strategy is the well documented and predictable chemo-, regio- and stereoselectivitiy of boron hydrides towards polyolefinic substrates. The overriding question which has generated this phase of our proposal deals with the stereochemistry of carbonylation (CO/cyanidation/carbanion insertion/etc.). To address this problem we propose the synthesis of pacifigorgo via Boron Annulation (stitching and riveting), the stereochemistry of the C-1 hydroxy1 group evolving from the riveting step. Based on the small amount of data available, we are predicting the formation of pacifigorgol from a boracyclane via carbonylation or equivalent process. We will explore the possibility that variations in riveting techniques might alter the stereochemical outcome of the boron replacement process. A major goal of this total synthesis is to present more insight into this carbon boron replacement process.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
2R01GM034896-02
Application #
3286710
Study Section
Medicinal Chemistry Study Section (MCHA)
Project Start
1985-09-12
Project End
1988-08-31
Budget Start
1986-09-01
Budget End
1987-08-31
Support Year
2
Fiscal Year
1986
Total Cost
Indirect Cost
Name
University of South Carolina at Columbia
Department
Type
Schools of Arts and Sciences
DUNS #
111310249
City
Columbia
State
SC
Country
United States
Zip Code
29208