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| LEADER |
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| 001 |
in00001558921 |
| 005 |
20220103134505.0 |
| 007 |
cr unu a |
| 008 |
000911s1999 xx a b 000 0 eng d |
| 035 |
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|a (OCoLC)ocm44992491
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| 040 |
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|a TXA
|c TXA
|d UtOrBLW
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| 049 |
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|a TXAM
|a TXAR
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| 099 |
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|a 1999
|a Thesis
|a J59
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| 100 |
1 |
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|a Johnson, Derrell W.,
|d 1973-
|
| 245 |
1 |
0 |
|a Nonlinear effects in kinetic resolutions /
|c by Derrell W. Johnson, Jr.
|
| 264 |
|
1 |
|a [Place of publication not identified] :
|b [publisher not identified] ;
|c 1999.
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| 300 |
|
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|a xii, 74 leaves :
|b illustrations ;
|c 28 cm.
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| 336 |
|
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|a text
|b txt
|2 rdacontent
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| 337 |
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|a computer
|b c
|2 rdamedia
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| 338 |
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|a online resource
|b cr
|2 rdacarrier
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| 500 |
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|a "Major subject: Chemistry".
|
| 500 |
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|a Vita.
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| 502 |
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|b M.S.
|c Texas A&M University
|d 1999.
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| 504 |
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|a Includes bibliographical references (leaves 70-73).
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| 520 |
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|a The impact of nonlinear effects in the asymmetric catalysis of kinetic resolutions is analyzed. It is found with minimal assumptions that the kinetics of homocompetitive reactions should apply generally to kinetic resolutions involving partially resolved catalysts, and this is supported by experimental observations with the Jacobsen hydrolytic kinetic resolution (HKR) of epoxides. The criterion for a nonlinear effect in asymmetric catalysis--a nonlinear correlation between the enantiomeric excess in a choral ligand and the product enantiomeric excess obtained from a reaction--is examined. The nonlinear effect idea is found to be generalizable to kinetic resolutions and other reactions by replacing consideration of the product enantiomeric excess with the quantity (k[]/k[]-1)/(k[]/k[]+1), a differential kinetic enantiomeric enhancement (DKEE). A nonlinear effect may then be defined by a nonlinear correlation between the DKEE and the chiral ligand enantiomeric excess. The application of these ideas to previously reported kinetic resolutions of sulfoxides and to nonlinear effects in the Jacobsen HKR is described. Relatively small nonlinear effects in kinetic resolutions are sufficient to obtain large asymmetric amplifications. A catalyst modification in the Jacobsen HKR also allows for the development of a novel recyclable system for the iterative enhancement of optical activity.
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| 530 |
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|a Also available online.
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| 530 |
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|a Issued also on microfiche from Lange Micrographics.
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| 650 |
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4 |
|a Major chemistry.
|
| 856 |
4 |
1 |
|u https://hdl.handle.net/1969.1/ETD-TAMU-1999-THESIS-J59
|z Link to OAKTrust copy
|t 0
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| 948 |
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|a cataloged
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|c 2000/9/12
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|t 0
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| 952 |
f |
f |
|p noncirc
|a Texas A&M University
|b College Station
|c Cushing Memorial Library & Archives
|s cush tdrm
|d Cushing: Theses & Dissertations Microforms (Does not check out)
|t 0
|e 1999 Thesis J59
|h Other scheme
|i computer -- online resource
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| 952 |
f |
f |
|a Texas A&M University
|b College Station
|c Electronic Resources
|s www_evans
|d Available Online
|t 0
|e 1999 Thesis J59
|h Other scheme
|
| 998 |
f |
f |
|a 1999 Thesis J59
|t 0
|l Available Online
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| 998 |
f |
f |
|a 1999 Thesis J59
|t 0
|l Cushing: Theses & Dissertations Microforms (Does not check out)
|