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Asymmetric synthesis by palladium (I...

Hamed, Othman A.

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Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system./
作者:	Hamed, Othman A.
面頁冊數:	149 p.
附註:	Source: Dissertation Abstracts International, Volume: 57-12, Section: B, page: 7524.
Contained By:	Dissertation Abstracts International57-12B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9715240
ISBN:	0591230313

Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system.
Hamed, Othman A.

Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system. - 149 p.

Source: Dissertation Abstracts International, Volume: 57-12, Section: B, page: 7524.

Thesis (Ph.D.)--Loyola University Chicago, 1997.

This proposal is divided into two Parts: (I) Exchange and oxidation of chiral allylic alcohols using chirality transfer. (II) Asymmetric synthesis using Pd(II) catalysts with chiral auxiliaries.

ISBN: 0591230313Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system.
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100 1 $a Hamed, Othman A. $3 1903236
245 1 0 $a Asymmetric synthesis by palladium (II) catalysis: Chirality transfer and new asymmetric catalytic system.
300 $a 149 p.
500 $a Source: Dissertation Abstracts International, Volume: 57-12, Section: B, page: 7524.
500 $a Director: Patrick M. Henry.
502 $a Thesis (Ph.D.)--Loyola University Chicago, 1997.
520 $a This proposal is divided into two Parts: (I) Exchange and oxidation of chiral allylic alcohols using chirality transfer. (II) Asymmetric synthesis using Pd(II) catalysts with chiral auxiliaries.
520 $a Part I is divided into two sections: (A) The determination of stereochemistries of hydroxypalladation using chirality transfer. (B) Preparation of trichiral molecules. The allylic alcohols used for these studies included (R)-( $- $) -Z- and E-3-hexen-2-ol (13a), (R)-( $- $) -Z-4-hexen-3-ol (13b), (R)-Z- and E-3-penten-2-ol (17). The chiral alcohols were prepared by reduction of the corresponding alkynones with alpine-borane reagent to give the alkynones which were reduced with either Lindlar's catalyst or LiAlH $\ sb4 $ to give the Z and E isomers respectively.
520 $a At low (Cl $\ sp- $) PdCl $\ sb4\sp{2-} $ oxidizes 13a to a mixture of (R)-Z-4-hydroxy-2-hexanone (15a) and (R)-5-hydroxy-3-hexanone (15b). The configuration of 15a was consistent with syn hydroxypalladation. At high (Cl $\ sp- $) ( $> $2 M) PdCl $\ sb4\sp{2-} $ isomerizes 13b to (S)-Z-13a. This result is most consistent with anti hydroxypalladation. Thus the modes of addition are opposite at high and low ( $) .
520 $a (R)-Z- and (R)-E-17 were tested as new stereochemical probes to readily determine the modes of addition of various Pd(II) reagents to olefins under a variety of reaction conditions. Reaction of these alcohols with nucleophiles such as hydroxy, methoxy, acetoxy, phenyl and carbomethoxy Pd(II) species gave the corresponding 2-pentanones whose absolute configuration indicated the modes of addition. Generally the modes of addition were as expected but there were some surprises which require further investigation.
520 $a The oxidation of (R)-Z- and (R)-E-17 by PdCl $\ sb4\sp{2-} $ under carbon monoxide pressure (3 atm.) produced 3,4-dicarbomethoxy-2-pentanols with 3 chiral centers. The chirality transfer to both the 3 and 4 positions was close to 100% for both geometric isomers. Tentative assignment of absolute configuration of the new chiral centers was carried out by NOE experiments. This reaction could be used to produce a number of new trichiral molecules.
520 $a In Part II two chiral syntheses are studied: (A) Phenylation of olefins (Heck reaction). (B) Oxidation of olefins by Pd(II) catalysts containing chiral ligands in the presence of CuCl $\ sb2 $ to give optically active chlorohydrins.
590 $a School code: 0112.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Organic. $3 516206
690 $a 0488
690 $a 0490
710 2 0 $a Loyola University Chicago. $3 1020295
773 0 $t Dissertation Abstracts International $g 57-12B.
790 1 0 $a Henry, Patrick M., $e advisor
790 $a 0112
791 $a Ph.D.
792 $a 1997
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9715240