There is an increasing need for the preparation of organic compounds as single enantiomers or diastereomers. This is an outgrowth of the requirement for pharmaceuticals to be single chiral entities. Thus the development of new methods for the preparation of enantiomerically pure compounds is important. This proposal describes strategies for obtaining high levels of rho and beta diastereoselectivity in radical reactions with acyclic systems. The proposed work focuses on understanding the factors responsible for selectivity in radical reactions such that future development of new synthetic strategies based on radical intermediates will be feasible. The study also addresses the issues of chiral catalysis in radical reactions, a methodology not available to the synthetic chemist at the present time. The goals of this proposal are: * The development of new strategies for obtaining high levels of acyclic diastereoselection in radical reactions. * The extension of these studies for the introduction of multiple chiral centers using radical methodologies. * The development of radical processes for the synthesis of acetate aldols, aldols, and beta-amino acids. * The development of enantioselective radical reactions using chiral Lewis acids. * The development of radical methods for carbon-carbon bond construction which are inaccessible by ionic methods.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM054656-02
Application #
2444906
Study Section
Medicinal Chemistry Study Section (MCHA)
Project Start
1996-07-01
Project End
2000-06-30
Budget Start
1997-07-01
Budget End
1998-06-30
Support Year
2
Fiscal Year
1997
Total Cost
Indirect Cost
Name
North Dakota State University
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
City
Fargo
State
ND
Country
United States
Zip Code
58108
Sibi, Mukund; Yang, Yong-Hua; Lee, Sunggi (2008) Tin-Free Enantioselective Radical Reactions Using Silanes. Org Lett :
Sibi, Mukund P; Hasegawa, Masayuki (2007) Organocatalysis in radical chemistry. Enantioselective alpha-oxyamination of aldehydes. J Am Chem Soc 129:4124-5
Sibi, Mukund P; Nad, Sukanya (2007) Enantioselective radical reactions: stereoselective aldol synthesis from cyclic ketones. Angew Chem Int Ed Engl 46:9231-4
Lee, Sunggi; Lim, Chae Jo; Kim, Sunggak et al. (2006) Enantioselective conjugate radical addition to alpha'-hydroxy enones. Org Lett 8:4311-3
Sibi, Mukund P; Zimmerman, Jake (2006) Pyrones to pyrans: enantioselective radical additions to acyloxy pyrones. J Am Chem Soc 128:13346-7
Sibi, Mukund P; He, Liwen (2006) Enantioselective Radical Reactions. Formation of Chiral Quaternary Centers. Synlett 2006:689-692
Sibi, Mukund P; Patil, Kalyani (2006) Enantioselective radical reactions. Evaluation of nitrogen protecting groups in the synthesis of beta-amino acids. Tetrahedron Asymmetry 17:516-519
Hein, Jason E; Zimmerman, Jake; Sibi, Mukund P et al. (2005) Stereoselective conjugate radical additions: application of a fluorous oxazolidinone chiral auxiliary for efficient tin removal. Org Lett 7:2755-8
Sibi, Mukund P; Patil, Kalyani (2005) Enantioselective H-atom transfer reaction: a strategy to synthesize formaldehyde aldol products. Org Lett 7:1453-6
Sibi, Mukund P; Petrovic, Goran; Zimmerman, Jake (2005) Enantioselective radical addition/trapping reactions with alpha,beta-disubstituted unsaturated imides. Synthesis of anti-propionate aldols. J Am Chem Soc 127:2390-1

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