Cyclizations in which the organopalladiums created in Heck reactions are trapped by either amines or the sodium salts of alcohols, are proposed. Ways to perform tandem Heck/carbon-heteroatom bond forming cascades with regio-, stereo-, and enantioselectivity are proposed. The use of acetylenes in place of the olefins, and tandem heterocycle/carbon- heteroatom bond forming reactions are proposed. The use of chiral amines as trapping nucleophiles is proposed, as is the use of internal amines/alcohols to form spirocyclic rings. The proposed reactions are based on successful procedures for the palladium catalyzed formation of aryl amines and aryl ethers, and cascade Heck reactions which use organometals, carbon monoxide, or hydride as the terminating agent. Conditions which were of importance in catalyzing these reactions (e.g. the use of chelating ligands such as BINAP in Pd-catalyzed C-N and C-O formation) will be the starting points in the search for conditions that will catalyze the proposed reactions. The development of such methodology would be significant, for it would provide a new way to quickly build complex structures from relatively simple substrates.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Postdoctoral Individual National Research Service Award (F32)
Project #
5F32GM019912-02
Application #
6178880
Study Section
Bio-Organic and Natural Products Chemistry Study Section (BNP)
Program Officer
Ikeda, Richard A
Project Start
2000-05-01
Project End
Budget Start
2000-05-01
Budget End
2001-04-30
Support Year
2
Fiscal Year
2000
Total Cost
$32,416
Indirect Cost
Name
Massachusetts Institute of Technology
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
City
Cambridge
State
MA
Country
United States
Zip Code
02139