| Type of Document |
Dissertation |
| Author |
DeGuzman, Joseph Christopher
|
| URN |
etd-06192006-161356 |
| Title |
Memory of Chirality in 1,4-Benzodiazepin-2-ones |
| Degree |
PhD |
| Department |
Chemistry |
| Advisory Committee |
| Advisor Name |
Title |
| Carlier, Paul R. |
Committee Chair |
| Etzkorn, Felicia A. |
Committee Member |
| Hanson, Brian E. |
Committee Member |
| Kingston, David G. I. |
Committee Member |
| Tanko, James M. |
Committee Member |
|
| Keywords |
- enolate
- axial chirality
- quaternary
- racemization
- benzodiazepine
- conformer
- Memory of chirality
- enantiomeric excess
- dynamic chirality
|
| Date of Defense |
2006-05-31 |
| Availability |
unrestricted |
Abstract
Memory of chirality (MOC) is an emerging strategy in asymmetric synthesis. It has been applied to enolate chemistry, reactions involving carbocation intermediates, and to radical systems. In this strategy the chirality of an enantiopure reactant is transferred to the dynamic chirality of a reactive intermediate to produce stereospecific product.
1,4-Benzodiazepin-2-ones have been described as a “privileged” structure in medicinal chemistry. In addition to their uses as anxiolytics (Valium ®) and anti-epileptic agents (Clonopin ®), they have shown activity as HIV Tat antagonist, ras farnesyltransferase inhibitors in cancer cells, and antiarrhythmic agents. Because of the utility of this scaffold in the area of medicinal chemistry, it has served as a template in libraries for tens of thousands of compounds. Despite the vast diversity of 1,4-benzodiazepin-2-ones, there are few routes to enantiomerically enriched 3,3-disubstituted benzodiazepines containing a “quaternary” stereogenic center. This research will discuss the stereochemical properties of 1,4-benzodiazepin-2-ones, and provide a novel approach to synthesize enantiomerically enriched “quaternary” benzodiazepines with stereogenic centers through MOC, without the use of external chiral sources.
|
| Files |
| Filename |
Size |
Approximate Download Time
(Hours:Minutes:Seconds)
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| 28.8 Modem |
56K Modem |
ISDN (64 Kb) |
ISDN (128 Kb) |
Higher-speed Access |
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Dissertation.pdf |
804.10 Kb |
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