語系:
繁體中文
English
說明(常見問題)
登入
回首頁
切換:
標籤
|
MARC模式
|
ISBD
Structure-Reactivity Relationships o...
~
Mack, Kyle Anthony.
Structure-Reactivity Relationships of Lithium Amides : = LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations.
紀錄類型:
書目-語言資料,手稿 : Monograph/item
正題名/作者:
Structure-Reactivity Relationships of Lithium Amides :/
其他題名:
LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations.
作者:
Mack, Kyle Anthony.
面頁冊數:
1 online resource (195 pages)
附註:
Source: Dissertation Abstracts International, Volume: 79-10(E), Section: B.
Contained By:
Dissertation Abstracts International79-10B(E).
標題:
Organic chemistry. -
電子資源:
click for full text (PQDT)
ISBN:
9780438025660
Structure-Reactivity Relationships of Lithium Amides : = LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations.
Mack, Kyle Anthony.
Structure-Reactivity Relationships of Lithium Amides :
LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations. - 1 online resource (195 pages)
Source: Dissertation Abstracts International, Volume: 79-10(E), Section: B.
Thesis (Ph.D.)--Cornell University, 2018.
Includes bibliographical references
Enolizations of highly substituted acyclic ketones used in the syntheses of tetrasubstituted olefin-based anticancer agents are described. Lithium hexamethyldisilazide (LiHMDS)-mediated enolizations are moderately Z-selective in neat tetrahydrofuran (THF) and E-selective in 2.0 M THF/hexane. The results of NMR spectroscopy show the resulting enolates to be statistically distributed ensembles of E,E-, E,Z-, and Z,Z-enolate dimers with subunits that reflect the selectivities. The results of rate studies trace the preference for E and Z isomers to tetrasolvated- and pentasolvated-monomer-based transition structures, respectively. Enolization using LiHMDS in N,N-dimethylethylamine or triethylamine in toluene affords a 65:1 mixture of LiHMDS?lithium enolate mixed dimers containing E and Z isomers, respectively. Spectroscopic studies show that condition-dependent complexation of ketone to LiHMDS occurs in trialkylamine/toluene. Rate data attribute the high selectivity exclusively to monosolvated-dimer-based transition structures.
Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2018
Mode of access: World Wide Web
ISBN: 9780438025660Subjects--Topical Terms:
1148722
Organic chemistry.
Index Terms--Genre/Form:
554714
Electronic books.
Structure-Reactivity Relationships of Lithium Amides : = LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations.
LDR
:03007ntm a2200349Ki 4500
001
917844
005
20181022132248.5
006
m o u
007
cr mn||||a|a||
008
190606s2018 xx obm 000 0 eng d
020
$a
9780438025660
035
$a
(MiAaPQ)AAI10744671
035
$a
(MiAaPQ)cornellgrad:10720
035
$a
AAI10744671
040
$a
MiAaPQ
$b
eng
$c
MiAaPQ
$d
NTU
100
1
$a
Mack, Kyle Anthony.
$3
1192023
245
1 0
$a
Structure-Reactivity Relationships of Lithium Amides :
$b
LiHMDS-Mediated Enolizations of Hindered Aryl Ketones and LiTMP-Mediated Ortholithiations.
264
0
$c
2018
300
$a
1 online resource (195 pages)
336
$a
text
$b
txt
$2
rdacontent
337
$a
computer
$b
c
$2
rdamedia
338
$a
online resource
$b
cr
$2
rdacarrier
500
$a
Source: Dissertation Abstracts International, Volume: 79-10(E), Section: B.
500
$a
Adviser: David B. Collum.
502
$a
Thesis (Ph.D.)--Cornell University, 2018.
504
$a
Includes bibliographical references
520
$a
Enolizations of highly substituted acyclic ketones used in the syntheses of tetrasubstituted olefin-based anticancer agents are described. Lithium hexamethyldisilazide (LiHMDS)-mediated enolizations are moderately Z-selective in neat tetrahydrofuran (THF) and E-selective in 2.0 M THF/hexane. The results of NMR spectroscopy show the resulting enolates to be statistically distributed ensembles of E,E-, E,Z-, and Z,Z-enolate dimers with subunits that reflect the selectivities. The results of rate studies trace the preference for E and Z isomers to tetrasolvated- and pentasolvated-monomer-based transition structures, respectively. Enolization using LiHMDS in N,N-dimethylethylamine or triethylamine in toluene affords a 65:1 mixture of LiHMDS?lithium enolate mixed dimers containing E and Z isomers, respectively. Spectroscopic studies show that condition-dependent complexation of ketone to LiHMDS occurs in trialkylamine/toluene. Rate data attribute the high selectivity exclusively to monosolvated-dimer-based transition structures.
520
$a
Rate and mechanistic studies of ortholithiations by lithium 2,2,6,6-tetramethylpiperidine focus on four arenes: 1,4-bis(trifluoromethyl)benzene, 1,3-bis(trifluoromethyl)benzene, 1,3-dimethoxybenzene, and 4,4-dimethyl-2-phenyl-2-oxazoline. Metalations occur via substrate-dependent combinations of monosolvated monomer, disolvated monomer, and tetrasolvated dimer (triple ions). Density functional theory computational studies augment the experimental data. We discuss the challenges presented by shifting dimer--monomer proportions in determining the observable reaction orders and our mathematical treatment of such shifting in reactant structure.
533
$a
Electronic reproduction.
$b
Ann Arbor, Mich. :
$c
ProQuest,
$d
2018
538
$a
Mode of access: World Wide Web
650
4
$a
Organic chemistry.
$3
1148722
650
4
$a
Chemistry.
$3
593913
655
7
$a
Electronic books.
$2
local
$3
554714
690
$a
0490
690
$a
0485
710
2
$a
ProQuest Information and Learning Co.
$3
1178819
710
2
$a
Cornell University.
$b
Chemistry & Chemical Biology.
$3
1192014
773
0
$t
Dissertation Abstracts International
$g
79-10B(E).
856
4 0
$u
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10744671
$z
click for full text (PQDT)
筆 0 讀者評論
多媒體
評論
新增評論
分享你的心得
Export
取書館別
處理中
...
變更密碼[密碼必須為2種組合(英文和數字)及長度為10碼以上]
登入