The objectives of this work are to develop new methods and strategies of carbon-carbon formation for the synthesis of biologically and medicinally important compounds. The emphasis is on the development of procedures for accomplishing multistep transformations in one pot operations. The work is divided into six sections: 1) The synthesis of polysubstituted aromatic compounds using zirconocene complexes of substituted benzynes and related species; 2) The use of zirconocene complexes of acyclic alkynes for the synthesis of cyclopentenones, 1,3-dienes, cyclobutenes as well as a variety of other useful organic compounds; 3) The use of cyclic alkyne complexes to prepare a variety of synthetically useful bicyclic compounds; 4) The synthesis of substituted cyclopropanes and cyclobutanes using zirconocene complexes of cyclopropene and cyclobutene; 5) The preparation of a variety of nitrogen containing compounds including pyrroles, pyrrolinones, lactams, allylic amines and 1,2- aminoalcohols through the vehicle of zirconocene complexes of imines; 6) The synthesis of a variety of interesting and useful organosulfur compounds using zirconocene complexes of thioaldehydes as intermediates.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM034917-07
Application #
3286803
Study Section
Medicinal Chemistry Study Section (MCHA)
Project Start
1985-04-01
Project End
1992-11-30
Budget Start
1991-04-01
Budget End
1992-11-30
Support Year
7
Fiscal Year
1991
Total Cost
Indirect Cost
Name
Massachusetts Institute of Technology
Department
Type
Schools of Arts and Sciences
DUNS #
City
Cambridge
State
MA
Country
United States
Zip Code
02139
Hyde, Alan M; Buchwald, Stephen L (2009) Synthesis of 5,5-disubstituted butenolides based on a Pd-catalyzed gamma-arylation strategy. Org Lett 11:2663-6
Chieffi, A; Kamikawa, K; Ahman, J et al. (2001) Catalytic asymmetric vinylation of ketone enolates. Org Lett 3:1897-900
Tomori, H; Fox, J M; Buchwald, S L (2000) An improved synthesis of functionalized biphenyl-based phosphine ligands. J Org Chem 65:5334-41
Hundertmark, T; Littke, A F; Buchwald, S L et al. (2000) Pd(PhCN)(2)Cl(2)/P(t-Bu)(3): a versatile catalyst for Sonogashira reactions of aryl bromides at room temperature. Org Lett 2:1729-31
Broene, R D; Buchwald, S L (1993) Zirconocene complexes of unsaturated organic molecules: new vehicles for organic synthesis. Science 261:1696-701