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Palladacycles with palladium-bonded ...

University of Kansas., Chemistry.

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Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry./
Author:	Hershberger, John Charles.
Description:	428 p.
Notes:	Adviser: Helena C. Malinakova.
Contained By:	Dissertation Abstracts International70-04B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3354839
ISBN:	9781109124231

Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry.
Hershberger, John Charles.

Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry. - 428 p.

Adviser: Helena C. Malinakova.

Thesis (Ph.D.)--University of Kansas, 2009.

Organometallic chemistry has undoubtedly changed the way synthetic chemists construct molecules as well as the way synthetic chemists think about constructing molecules. Three well-known and most widely used transition metal-catalyzed reactions are the cross-coupling reactions, the Heck reaction, and olefin metathesis. Reactions stoichiometric in the transition-metal played an important role in their development, providing insight that could have remained uncovered otherwise.

ISBN: 9781109124231Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry.
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020 $a 9781109124231
035 $a (UMI)AAI3354839
035 $a AAI3354839
040 $a UMI $c UMI
100 1 $a Hershberger, John Charles. $3 1064720
245 1 0 $a Palladacycles with palladium-bonded stereogenic carbons: Tools for exploring reaction pathways in organometallic chemistry.
300 $a 428 p.
500 $a Adviser: Helena C. Malinakova.
500 $a Source: Dissertation Abstracts International, Volume: 70-04, Section: B, page: 2309.
502 $a Thesis (Ph.D.)--University of Kansas, 2009.
520 $a Organometallic chemistry has undoubtedly changed the way synthetic chemists construct molecules as well as the way synthetic chemists think about constructing molecules. Three well-known and most widely used transition metal-catalyzed reactions are the cross-coupling reactions, the Heck reaction, and olefin metathesis. Reactions stoichiometric in the transition-metal played an important role in their development, providing insight that could have remained uncovered otherwise.
520 $a The first goal of this dissertation is to expand our understanding of how changing the ligand sphere around the palladium center (by utilizing a triphenylphosphine moiety attached to an insoluble polymer support) affects the reactivity of the palladacycles on solid-phase. More specifically, we compared the reactivity of polymer-bound palladacycles to their soluble triphenylphosphine analogs. The second goal of this dissertation is to elucidate how a carbon stereocenter bound to palladium transfers its asymmetry to a second newly formed stereocenter that is also bound to palladium, and the role played by the auxiliary ligand in this process.
520 $a The first project detailed in this dissertation describes a basic study of the interactions between a solid-phase support and well-defined palladacycles. The effects of phosphorus loading, palladium loading, P : Pd ratio, and polymer swelling on the reactivity of the polymer-bound palladacycles were explored. The results of these studies as well as the facile syntheses of 2H-1 -benzopyrans are presented. We also attempted the synthesis of a library of highly substituted 1,2-dihydroquinolines utilizing this solid-phase technology. Although we were unable to successfully complete the library synthesis, future studies in this area are expected to further elucidate the difference in the reactivities of solid-phase oxa-palladacycles and solid-phase aza-palladacycles.
520 $a The second project describes the successful development of an expeditious route to palladapyrrolidinones, a new organometallic scaffold featuring two Csp3-hybridized stereogenic carbons attached to a palladium center. These are rare examples of palladium complexes bearing two stereogenic carbons bound to a palladium center. It is also the first system in which the effect of an existing carbon stereocenter bound directly to a palladium center upon the formation of a second stereocenter also directly bound to palladium can be studied in detail. Up to 20 : 1 diastereoselectivity was observed during the formation of the second stereocenter and the diastereoselectivity is shown to be ligand-dependent, indicating that the auxiliary ligand sphere plays a significant role in diastereoinduction. Rather unexpectedly, utilizing a chiral non-racemic ligand in the synthesis of palladapyrrolidinones had little effect on the diastereoselectivity of the reaction. A model to explain the diastereoselectivity and the surprising lack of influence of the chiral non-racemic ligand on the diastereoselectivity is proposed based on X-ray structural studies.
590 $a School code: 0099.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Organic. $3 516206
690 $a 0488
690 $a 0490
710 2 $a University of Kansas. $b Chemistry. $3 1017723
773 0 $t Dissertation Abstracts International $g 70-04B.
790 $a 0099
790 1 0 $a Barybin, Mikhail V. $e committee member
790 1 0 $a Givens, Richard S. $e committee member
790 1 0 $a Malinakova, Helena C. $e committee member
790 1 0 $a Malinakova, Helena C., $e advisor
790 1 0 $a Prisinzano, Thomas E. $e committee member
790 1 0 $a Tunge, Jon A. $e committee member
791 $a Ph.D.
792 $a 2009
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3354839