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Development of transition metal Lewi...
~
Hollis, Thedford Keith.
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Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions./
作者:
Hollis, Thedford Keith.
面頁冊數:
119 p.
附註:
Source: Dissertation Abstracts International, Volume: 56-03, Section: B, page: 1410.
Contained By:
Dissertation Abstracts International56-03B.
標題:
Chemistry, Inorganic. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9523499
Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions.
Hollis, Thedford Keith.
Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions.
- 119 p.
Source: Dissertation Abstracts International, Volume: 56-03, Section: B, page: 1410.
Thesis (Ph.D.)--The University of Chicago, 1995.
The metallocene complexes (TiCpSubjects--Topical Terms:
517253
Chemistry, Inorganic.
Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions.
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Development of transition metal Lewis acids. The mechanisms of the Mukaiyama aldol and Sakurai allylation reactions.
300
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119 p.
500
$a
Source: Dissertation Abstracts International, Volume: 56-03, Section: B, page: 1410.
500
$a
Adviser: Brice Bosnich.
502
$a
Thesis (Ph.D.)--The University of Chicago, 1995.
520
$a
The metallocene complexes (TiCp
$\
sbsp{2}{\*}
$(
H
$\
sb2
$\
sb2
$)
, (TiCp
$\
sb2
$\
sb2
$)
, and (ZrCp
$\
sb2
$\
sb2
$(
THF)) have been shown to be effective catalysts for the Diels-Alder reaction of
$\
alpha,\beta
$-
unsaturated aldehydes and ketones with cyclic and acyclic dienes. This catalysis was shown to occur via Lewis acid catalysis and not Bronsted acid catalysis. These catalysts were found to catalyze slowly the polymerization of dienes. Application of an asymmetric analogue of these catalysts provided only low enantiomeric excesses. (TiCp
$\
sb2
$\
sb2
$)
and (ZrCp
$\
sb2
$\
sb2
$(
THF)) have been shown to be efficient catalysts for a wide range of Mukaiyama aldol and Sakurai allylation reactions. Application of the chiral metallocenes (S,S)- (Ti((R,R)-cyclacene)OTf
$\
sb2
$)
and (Ti(S-biphenacene)(H
$\
sb2
$\
sb2
$)
OTf
$\
sb2
$
to these reactions resulted in no asymmetric induction. These observations led to an investigation of the mechanisms of catalysis for these reactions. (TiCp
$\
sb2
$\
sb2
$)
, Ph
$\
sb3
$\
sb3
$\
sb4
$
were investigated as catalysts. (TiCp
$\
sb2
$\
sb2
$)
was found to react with water which resulted in the cleavage of the enol silane or allylsilane to give Me
$\
sb3
$\
sb3
$\
sb3
$\
sb2
$\
sb2
$)
employing acetals as the electrophiles showed that Me
$\
sb3
$\
sb3
$\
sb3
$\
sb3
$\
sb4
$
was investigated as a catalyst for the Sakurai allylation reaction and was found, in the absence of the acid hydrolysis pathway, to generate Me
$\
sb3
$\
sb4
$,
a potent catalyst, by reaction with the allylsilane. Me
$\
sb3
590
$a
School code: 0330.
650
4
$a
Chemistry, Inorganic.
$3
517253
650
4
$a
Chemistry, Organic.
$3
516206
690
$a
0488
690
$a
0490
710
2 0
$a
The University of Chicago.
$3
1017389
773
0
$t
Dissertation Abstracts International
$g
56-03B.
790
1 0
$a
Bosnich, Brice,
$e
advisor
790
$a
0330
791
$a
Ph.D.
792
$a
1995
856
4 0
$u
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9523499
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