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Substrate scope of the asymmetric bi...

Mulrooney, Carol A.

Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin.
Author:	Mulrooney, Carol A.
Description:	278 p.
Notes:	Adviser: Marisa C. Kozlowski.
Notes:	Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3806.
Contained By:	Dissertation Abstracts International67-07B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3225509
ISBN:	9780542799846

Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin.
Mulrooney, Carol A.

Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin. - 278 p.

Adviser: Marisa C. Kozlowski.

Thesis (Ph.D.)--University of Pennsylvania, 2006.

*Please refer to dissertation for diagrams.

ISBN: 9780542799846Subjects--Topical Terms:

193634
Chemistry, Organic.

Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin.
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100 0 $a Mulrooney, Carol A. $3 264201
245 1 0 $a Substrate scope of the asymmetric biaryl coupling reaction. Asymmetric synthesis of a perylenequinone. Progress toward the synthesis of cercosporin.
300 $a 278 p.
500 $a Adviser: Marisa C. Kozlowski.
500 $a Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3806.
502 $a Thesis (Ph.D.)--University of Pennsylvania, 2006.
520 # $a *Please refer to dissertation for diagrams.
520 # $a Steps toward the synthesis of the natural product cercosporin were then developed. A mild decarboxylation reaction was employed to remove the methyl esters that were necessary for asymmetric biaryl coupling but not present in the natural product. An allyl group was introduced in the C7 position that would be later used to introduce the chiral alcohols in the side chains. The 7-membered ring present in cercosporin was introduced by C5/C5' hydroxylation, then a selective deprotection strategy followed by methylenation yielded intermediate 124. Initial studies toward the introduction of the C7/C7' chiral secondary alcohols proved disappointing. A survey of chiral reductions was initiated on a model system with moderate enantioselectivities achieved. Future plans are proposed to introduce the chiral secondary alcohol via reduction of a ketone with various chiral ligands.*
520 # $a The Kozlowski group has developed an asymmetric copper-catalyzed oxidative biaryl coupling reaction using a novel 1,5-diaza-cis-decalin ligand. This reaction gives good yields and enantioselectivities for a number of 3-substituted 2-naphthols to yield new BINOL derivatives. A substrate scope has been explored yielding insight into the utility and reaction mechanism. Compounds that have chelating groups in the 3-position are optimal for biaryl coupling. A series of 3-sulfone-2-naphthols is described for this reaction. The geometry and the electron-withdrawing character of the substituent are important for optimal coupling. The oxidation potential of the naphthol is important for oxidation, electron-donating substituents placed in the system have an effect on the yield and enantioselectivity of the reaction.*
520 # $a To explore the utility of the reaction further toward the synthesis of natural products and their derivatives, a series of highly substituted 2-naphthols was synthesized in order to explore the synthesis of perylenequinone natural products. Building on previously established successful biaryl couplings of highly substituted 2-naphthols, a model system was developed toward the synthesis of a perylenequinone derivative with the axial chirality as the only chiral element. Initial progress via an ortho-quinone led to racemized product. A nucleophilic aromatic substitution reaction was utilized to provide the oxygenation needed to transform the highly substituted biaryl 47 to a chiral perylenequinone.*
590 $a School code: 0175.
650 # 0 $a Chemistry, Organic. $3 193634
690 $a 0490
710 0 # $a University of Pennsylvania. $3 212781
773 0 # $g 67-07B. $t Dissertation Abstracts International
790 $a 0175
790 1 0 $a Kozlowski, Marisa C., $e advisor
791 $a Ph.D.
792 $a 2006
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