Nonlinear effects in kinetic resolutions /

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 experimen...

Full description

Bibliographic Details
Main Author: Johnson, Derrell W., 1973-
Format: Thesis eBook
Language:English
Published: [Place of publication not identified] : [publisher not identified] ; 1999.
Subjects:
Online Access:Link to OAKTrust copy

MARC

Tag First Indicator Second Indicator Subfields
LEADER 00000ctm a2200000Ka 4500
001 in00001558921
005 20220103134505.0
007 cr unu a
008 000911s1999 xx a b 000 0 eng d
035 |a (OCoLC)ocm44992491 
040 |a TXA  |c TXA  |d UtOrBLW 
049 |a TXAM  |a TXAR 
099 |a 1999  |a Thesis  |a J59 
100 1 |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. 
300 |a xii, 74 leaves :  |b illustrations ;  |c 28 cm. 
336 |a text  |b txt  |2 rdacontent 
337 |a computer  |b c  |2 rdamedia 
338 |a online resource  |b cr  |2 rdacarrier 
500 |a "Major subject: Chemistry". 
500 |a Vita. 
502 |b M.S.  |c Texas A&M University  |d 1999. 
504 |a Includes bibliographical references (leaves 70-73). 
520 |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. 
530 |a Also available online. 
530 |a Issued also on microfiche from Lange Micrographics. 
650 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 
948 |a cataloged  |b h  |c 2000/9/12  |d c  |e eneff  |f 11:01:04 am 
994 |a E0  |b TXA 
999 |a MARS 
999 f f |s 920bb25e-8347-38cb-a1d8-e2b79309aec9  |i 9ea09a0c-e72b-37e2-95b9-6f113e7b5ac7  |t 0 
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 
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 
998 f f |a 1999 Thesis J59  |t 0  |l Cushing: Theses & Dissertations Microforms (Does not check out)