The development of new methods that result in the formation of carbon-hetero bonds is synthetically challenging. Current technologies to access these important bonds rely on extensive functional group manipulation or employ sensitive transition metal complexes. A powerful solution to address these limitations would be the development of selective C-H methylene activation by cationic platinum(ll) complexes. The ability to directly transform a C-H bond into a carbon-heteroatom bond would dramatically alter current perceptions about bond formation. The mild reaction conditions of the Shilov oxidation are a significant advantage for the use of cationic platinum(ll) complexes. An approach that utilizes cationic Pt(ll) complexes for the regio- and enantioselective functionalization of benzylic methylene C-H bonds is outlined within this proposal. Reaction conditions and Iigands that facilitate regioselective methylene C-H activation will be identified through mechanistic experiments designed to evaluate stereoselectivity. After regioselective benzylic C-H activation is realized, formation of carbon-heteroatom and carbon-carbon bonds from well-defined platinum organometallic complexes will be attempted. The reaction will be made catalytic in platinum through the use of stoichiometric copper. When appropriate chiral, non-racemic ligands are employed, this sequence should be capable of asymmetric catalysis. Ultimately, this method is envisioned to allow direct asymmetric transformation of benzy!ic methylene C-H bonds into carbon-hetero or C-C bonds. ? ?

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Postdoctoral Individual National Research Service Award (F32)
Project #
1F32GM070272-01
Application #
6742371
Study Section
Special Emphasis Panel (ZRG1-F04 (20))
Program Officer
Lograsso, Philip
Project Start
2004-04-05
Project End
2006-04-04
Budget Start
2004-04-05
Budget End
2005-04-04
Support Year
1
Fiscal Year
2004
Total Cost
$41,068
Indirect Cost
Name
California Institute of Technology
Department
Type
Schools of Engineering
DUNS #
009584210
City
Pasadena
State
CA
Country
United States
Zip Code
91125