Although the Nazarov cyclization is a widely used method for the synthesis of cyclopentyl ring systems, the lack of a general strategy for production of enantiopure products from this reaction detracts from its synthetic utility. This proposal seeks to develop a general method for enantioselective organocatalytic Nazarov cyclizations through the use of a chiral secondary amine catalyst. The proposed strategy relies upon iminium activation of the divinyl ketone substrates followed by a torquoselective ring closure to generate a 2-aminoallyl cation intermediate, which can be trapped intramolecularly with a variety of nucleophilic alkenes or aryl groups. Structurally diverse and stereochemicalty complex fused and bridged polycyclic products may be accessed from achiral, acyclic components via this methodology. These products may serve as building blocks for a variety of cyclopentanoid and terpene natural products. ? ?

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Postdoctoral Individual National Research Service Award (F32)
Project #
5F32GM066595-02
Application #
6792186
Study Section
Special Emphasis Panel (ZRG1-F04 (20))
Program Officer
Marino, Pamela
Project Start
2003-09-01
Project End
2005-03-09
Budget Start
2004-09-01
Budget End
2005-03-09
Support Year
2
Fiscal Year
2004
Total Cost
$25,174
Indirect Cost
Name
California Institute of Technology
Department
Type
Schools of Engineering
DUNS #
009584210
City
Pasadena
State
CA
Country
United States
Zip Code
91125