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Part I. Asymmetric alkylation of alp...

Fennie, Michael W., Jr.

Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins.
Author:	Fennie, Michael W., Jr.
Description:	489 p.
Notes:	Adviser: Marisa C. Kozlowski.
Notes:	Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3800.
Contained By:	Dissertation Abstracts International67-07B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3225457
ISBN:	9780542798924

Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins.
Fennie, Michael W., Jr.

Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins. - 489 p.

Adviser: Marisa C. Kozlowski.

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

*Please refer to dissertation for diagrams.

ISBN: 9780542798924Subjects--Topical Terms:

193634
Chemistry, Organic.

Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins.
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100 0 $a Fennie, Michael W., Jr. $3 264193
245 1 0 $a Part I. Asymmetric alkylation of alpha-ketoesters and alpha-iminoesters using bifunctional catalysts. Part II. Strategies for the synthesis of the spirocyclic cores of the rubromycins.
300 $a 489 p.
500 $a Adviser: Marisa C. Kozlowski.
500 $a Source: Dissertation Abstracts International, Volume: 67-07, Section: B, page: 3800.
502 $a Thesis (Ph.D.)--University of Pennsylvania, 2006.
520 # $a *Please refer to dissertation for diagrams.
520 # $a A number of strategies were investigated for the synthesis of a bisphenolic spiroketal with electronic properties similar to that of the rubromycin family of natural products. Pleasingly, a diketone model system (30) underwent acid-catalyzed spirocyclization to afford a spiroketal.*
520 # $a Bifunctional catalysts were explored in the addition of Et2Zn to alpha-ketoesters (3). A variety of new ligands were synthesized and tested in the addition of Et2Zn to methyl benzoylformate. Upon examining reaction conditions with the amino salen catalyst, it was found that increasing the amount of Ti(Oi-Pr), in the reaction had a positive effect on the enantioselectivities (6 to 7).*
520 # $a Examining substrates that are less sterically encumbered resulted in the asymmetric catalytic alkylation of glyoxalate aldiminoesters (17 ) with good selectivity.*
520 # $a Part I. Bifunctional catalysts can position two reactants in close proximity and with the correct relative geometry to facilitate a reaction in a manner similar to some enzyme catalysts.(1).*
520 # $a Part II. Members of the rubromycin family of natural products are shown below. Efforts focused on the synthesis of the unique 5,6-bisphenolic spiroketals that join highly functionalized naphthazarin and isocoumarin subunits.*
520 # $a The asymmetric alkylation of alpha-ketiminoesters was explored using bifunctional amino-salen catalysts. In order to increase the desired reactivity, cyclic substrates were examined (15). With these geometrically stable imines, background reactivity was eliminated. Good yield and selectivity, however, was only achieved with the least sterically encumbered substrate.*
520 # $a The synthesis of a new naphthalene (32) was devised which (1) was shorter than previous syntheses, (2) avoided ortho -quinone methide side reactions, and (3) provided a handle to install an advanced diketone moeity.*
520 # $a This dissertation describes efforts in both reaction methodology as well as natural product synthesis.
520 # $a This naphthalene was brought forward in the synthesis of purpuromycin, but the synthesis has not yet been achieved due to extenuating steric and electronic factors associated with the system. Methods to circumvent these problems have been proposed and will be explored in the future.*
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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