Methods for synthesis of optically pure boron complexes, amino acids, amides, and esters are proposed. The critical new feature of the method depends on control of boron stereochemistry in a chiral """"""""ate"""""""" complex by crystal lattice effects. The cyclic """"""""ate"""""""" complex obtained from the boron reagent and a chiral difunctional substrate is formed as a mixture of diastereomers, but crystallization allows complete conversion into one crystalline isomer. Subsequent chemical transformations would be performed below the temperature for diastereomer interconversion via reversible """"""""ate"""""""" complex dissociation, and would take advantage of the """"""""asymmetric memory"""""""" of temporarily stereogenic boron. Applications of this concept to the synthesis of natural and unnatural amino acids are described, including methods for catalytic enolate alkylation. A new method for enantiocontrolled enolate protonation is proposed using Lewis acid induced internal proton return. Finally, some of the above methods will be used in short routes to specific chiral atropisomers and unusual chiral boron catalysts.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM044724-04
Application #
2182706
Study Section
Bio-Organic and Natural Products Chemistry Study Section (BNP)
Project Start
1991-08-01
Project End
1995-07-31
Budget Start
1994-08-01
Budget End
1995-07-31
Support Year
4
Fiscal Year
1994
Total Cost
Indirect Cost
Name
University of Wisconsin Madison
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
161202122
City
Madison
State
WI
Country
United States
Zip Code
53715