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Asymmetric synthesis of all-carbon a...

Asad, Md. Sharif A.

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Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks./
Author:	Asad, Md. Sharif A.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2015,
Description:	311 p.
Notes:	Source: Dissertation Abstracts International, Volume: 77-03(E), Section: B.
Contained By:	Dissertation Abstracts International77-03B(E).
Subject:	Organic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3732446
ISBN:	9781339193946

Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks.
Asad, Md. Sharif A.

Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks. - Ann Arbor : ProQuest Dissertations & Theses, 2015 - 311 p.

Source: Dissertation Abstracts International, Volume: 77-03(E), Section: B.

Thesis (Ph.D.)--The University of Wisconsin - Milwaukee, 2015.

This item is not available from ProQuest Dissertations & Theses.

The development of catalytic, enantioselective methods for the construction of all-carbon quaternary stereocenters is an outstanding achievement in the recent history of organic chemistry. The palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) reaction has played a key role in creating such stereocenters and has allowed researchers to synthesize a vast number of biologically potent natural products. However, synthetic methodologies to access compounds containing alpha-aryl groups to the quaternary carbon stereocenters are still rare. The increasing appearance of these all-carbon alpha-aryl quaternary stereocenters in a growing number of biologically active natural products and pharmaceutical agents creates a pressing need for the ability to construct this important motif enantioselectively. In this endeavor, a set of acyclic all-carbon alpha-aryl quaternary stereocenter has been synthesized via intermolecular Palladium catalyzed Asymmetric Allylic Alkylation (Pd-AAA). Here hydroxyacrylate was used as an unprecedented nucleophilic counterpart instead of the widely used ketonic substrate. This produced a very rare all-carbon quaternary aldehydes with good to excellent yields (75--99%) and enantioselectivities ranges between 75--94%. This methodology is not only limited to produce aldehydes, as an analogous ketone with a quaternary alpha-carbon center has also been synthesized successfully. Using this methodology, chiral 3,3 '-disubstituted oxindole moiety was produced with high yield (80%) and enantioselectivity (82%) from o-nitrophenylhydroxyacrylate in three simple steps. The oxindole framework bearing a tetrasubstituted carbon stereocenter at 3-position is a privileged heterocyclic motif that constructs the core of a large family of bioactive natural products and a series of pharmaceutically active compounds. An intensive research has been conducted to synthesize 3,3 '-disubstituted oxindole which resulted in a fair amount of methods to produce such an important moiety. However, to the best of our knowledge, all of the reported methodologies so far have used pre-formed oxindole ring itself or a highly specialized compound as a prochiral starting material to produce asymmetry. Another application of this method includes the synthesis of chiral alpha-disubstituted quaternary beta-lactone from the parent phenylhydroxyacrylate in high yield (87%) and enantioselectivity (94%). beta-lactones have recently emerged as important synthetic targets due to their occurrence in a variety of natural products, their utility as versatile synthetic intermediates, and their use as monomers for the preparation of biodegradable polymers.

ISBN: 9781339193946Subjects--Topical Terms:

523952
Organic chemistry.

Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks.
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100 1 $a Asad, Md. Sharif A. $3 3286618
245 1 0 $a Asymmetric synthesis of all-carbon alpha-aryl quaternary carbonyl compounds by palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) and their application to the synthesis of biologically important 3,3 '-disubstituted oxindole and alpha-disubstituted quaternary beta-lactone frameworks.
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300 $a 311 p.
500 $a Source: Dissertation Abstracts International, Volume: 77-03(E), Section: B.
500 $a Adviser: M. Mahmun Hossain.
502 $a Thesis (Ph.D.)--The University of Wisconsin - Milwaukee, 2015.
506 $a This item is not available from ProQuest Dissertations & Theses.
520 $a The development of catalytic, enantioselective methods for the construction of all-carbon quaternary stereocenters is an outstanding achievement in the recent history of organic chemistry. The palladium-catalyzed asymmetric allylic alkylation (Pd-AAA) reaction has played a key role in creating such stereocenters and has allowed researchers to synthesize a vast number of biologically potent natural products. However, synthetic methodologies to access compounds containing alpha-aryl groups to the quaternary carbon stereocenters are still rare. The increasing appearance of these all-carbon alpha-aryl quaternary stereocenters in a growing number of biologically active natural products and pharmaceutical agents creates a pressing need for the ability to construct this important motif enantioselectively. In this endeavor, a set of acyclic all-carbon alpha-aryl quaternary stereocenter has been synthesized via intermolecular Palladium catalyzed Asymmetric Allylic Alkylation (Pd-AAA). Here hydroxyacrylate was used as an unprecedented nucleophilic counterpart instead of the widely used ketonic substrate. This produced a very rare all-carbon quaternary aldehydes with good to excellent yields (75--99%) and enantioselectivities ranges between 75--94%. This methodology is not only limited to produce aldehydes, as an analogous ketone with a quaternary alpha-carbon center has also been synthesized successfully. Using this methodology, chiral 3,3 '-disubstituted oxindole moiety was produced with high yield (80%) and enantioselectivity (82%) from o-nitrophenylhydroxyacrylate in three simple steps. The oxindole framework bearing a tetrasubstituted carbon stereocenter at 3-position is a privileged heterocyclic motif that constructs the core of a large family of bioactive natural products and a series of pharmaceutically active compounds. An intensive research has been conducted to synthesize 3,3 '-disubstituted oxindole which resulted in a fair amount of methods to produce such an important moiety. However, to the best of our knowledge, all of the reported methodologies so far have used pre-formed oxindole ring itself or a highly specialized compound as a prochiral starting material to produce asymmetry. Another application of this method includes the synthesis of chiral alpha-disubstituted quaternary beta-lactone from the parent phenylhydroxyacrylate in high yield (87%) and enantioselectivity (94%). beta-lactones have recently emerged as important synthetic targets due to their occurrence in a variety of natural products, their utility as versatile synthetic intermediates, and their use as monomers for the preparation of biodegradable polymers.
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