國立高雄大學圖資館 |

Language: English

Back

Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations :Isolation and reactivity of catalytic intermediates.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations :
Reminder of title:	Isolation and reactivity of catalytic intermediates.
Author:	Stambuli, James Patrick.
Description:	286 p.
Notes:	Director: John F. Hartwig.
Notes:	Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4936.
Contained By:	Dissertation Abstracts International64-10B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3109468
ISBN:	0496570102

Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations :Isolation and reactivity of catalytic intermediates.
Stambuli, James Patrick.

Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations :Isolation and reactivity of catalytic intermediates. [electronic resource] - 286 p.

Director: John F. Hartwig.

Thesis (Ph.D.)--Yale University, 2003.

A high-throughput screening assay for the discovery of catalysts for transition metal-catalyzed cross-coupling reactions was developed. The assay was based on fluorescence resonance energy transfer (FRET) that occurred between a fluorophore and a quencher molecule. To screen catalysts for the Heck reaction, a base and catalyst were added to a solution of a dansyl flurophore that contained an olefin and a diazo quencher molecule that contained an aryl bromide. The decrease of fluorescence emission, as detected by a fluorescence spectrometer that is capable of analyzing a 96-well plate reader, allowed for the rapid determination of catalyst activity. From these results, the first room-temperature Heck reaction of aryl bromides was discovered. A mechanistic investigation of the active catalyst in this room-temperature Heck reaction led to the discovery of a palladium(I) dimeric complex that catalyzed the coupling of an aryl chloride and amine or an aryl bromide and boronic acid in less than 15 min at room temperature. This mechanistic investigation also led to the discovery of three-coordinate arylpalladium(II) halide complexes containing one dative ligand that are stabilized by weak agostic interactions. A series of these complexes of the general formula, LPd(Ar)(X), were prepared with L = 1-AdPtBu 2, PtBu3, or FcP tBu2(Ph)5 and X = Br, Cl, I, or OTf. Starting from these monomeric complexes, three-coordinate complexes that appear on the proposed catalytic cycles for the palladium-catalyzed etherification and amination of aryl halides were synthesized. The reactivity of these complexes provided evidence of their intermediacy in palladium-catalyzed cross-coupling reactions. In addition, the first reductive elimination of ether from an isolated, monomeric palladium alkoxide complex was observed.

ISBN: 0496570102Subjects--Topical Terms:

193634
Chemistry, Organic.

Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations :Isolation and reactivity of catalytic intermediates.
LDR:02864nmm _2200253 _450 001 162300
005 20051017073432.5
008 230606s2003 eng d
020 $a 0496570102
035 $a 00148801
035 $a 162300
040 $a UnM $c UnM
100 0 $a Stambuli, James Patrick. $3 227427
245 1 0 $a Discovery and development of transition metal catalysts for carbon-carbon and carbon-heteroatom bond formations : $b Isolation and reactivity of catalytic intermediates. $h [electronic resource]
300 $a 286 p.
500 $a Director: John F. Hartwig.
500 $a Source: Dissertation Abstracts International, Volume: 64-10, Section: B, page: 4936.
502 $a Thesis (Ph.D.)--Yale University, 2003.
520 # $a A high-throughput screening assay for the discovery of catalysts for transition metal-catalyzed cross-coupling reactions was developed. The assay was based on fluorescence resonance energy transfer (FRET) that occurred between a fluorophore and a quencher molecule. To screen catalysts for the Heck reaction, a base and catalyst were added to a solution of a dansyl flurophore that contained an olefin and a diazo quencher molecule that contained an aryl bromide. The decrease of fluorescence emission, as detected by a fluorescence spectrometer that is capable of analyzing a 96-well plate reader, allowed for the rapid determination of catalyst activity. From these results, the first room-temperature Heck reaction of aryl bromides was discovered. A mechanistic investigation of the active catalyst in this room-temperature Heck reaction led to the discovery of a palladium(I) dimeric complex that catalyzed the coupling of an aryl chloride and amine or an aryl bromide and boronic acid in less than 15 min at room temperature. This mechanistic investigation also led to the discovery of three-coordinate arylpalladium(II) halide complexes containing one dative ligand that are stabilized by weak agostic interactions. A series of these complexes of the general formula, LPd(Ar)(X), were prepared with L = 1-AdPtBu 2, PtBu3, or FcP tBu2(Ph)5 and X = Br, Cl, I, or OTf. Starting from these monomeric complexes, three-coordinate complexes that appear on the proposed catalytic cycles for the palladium-catalyzed etherification and amination of aryl halides were synthesized. The reactivity of these complexes provided evidence of their intermediacy in palladium-catalyzed cross-coupling reactions. In addition, the first reductive elimination of ether from an isolated, monomeric palladium alkoxide complex was observed.
590 $a School code: 0265.
650 # 0 $a Chemistry, Organic. $3 193634
650 # 0 $a Chemistry, Inorganic. $3 197298
710 0 # $a Yale University. $3 212430
773 0 # $g 64-10B. $t Dissertation Abstracts International
790 $a 0265
790 1 0 $a Hartwig, John F., $e advisor
791 $a Ph.D.
792 $a 2003
856 4 0 $u http://libsw.nuk.edu.tw/login?url=http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3109468 $z http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3109468