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Metal-catalyzed asymmetric synthesis...

Dartmouth College., Chemistry.

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Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines .

Record Type:	Electronic resources : Monograph/item
Title/Author:	Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines ./
Author:	Anderson, Brian Joseph.
Description:	552 p.
Notes:	Adviser: David S. Glueck.
Contained By:	Dissertation Abstracts International69-10B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3334062
ISBN:	9780549858034

Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines .
Anderson, Brian Joseph.

Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines . - 552 p.

Adviser: David S. Glueck.

Thesis (Ph.D.)--Dartmouth College, 2008.

Chapter One. Platinum-Catalyzed Asymmetric Alkylation of Bis(secondary) Phosphines. Efficient Screening and the Synthesis of an Enantiomerically Pure C2-Symmetric Diphosphine. Platinum-catalyzed asymmetric alkylation of secondary phosphines is a useful method for synthesis of a variety of novel chiral phosphines and bisphosphines. We have developed efficient methodology for rapid screening of Pt catalyst precursors and benzyl halides in alkylation of bis(secondary) phosphines (RHP&sim;PHR). Enantiomerically pure P(Ph)(o-CF3CH2C6H 4)(CH2)2P(Ph)(o-CF3CH 2C6H4) was isolated.

ISBN: 9780549858034Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines .
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020 $a 9780549858034
035 $a (UMI)AAI3334062
035 $a AAI3334062
040 $a UMI $c UMI
100 1 $a Anderson, Brian Joseph. $3 1029797
245 1 0 $a Metal-catalyzed asymmetric synthesis of P-stereogenic phosphines .
300 $a 552 p.
500 $a Adviser: David S. Glueck.
500 $a Source: Dissertation Abstracts International, Volume: 69-10, Section: B, page: 6090.
502 $a Thesis (Ph.D.)--Dartmouth College, 2008.
520 $a Chapter One. Platinum-Catalyzed Asymmetric Alkylation of Bis(secondary) Phosphines. Efficient Screening and the Synthesis of an Enantiomerically Pure C2-Symmetric Diphosphine. Platinum-catalyzed asymmetric alkylation of secondary phosphines is a useful method for synthesis of a variety of novel chiral phosphines and bisphosphines. We have developed efficient methodology for rapid screening of Pt catalyst precursors and benzyl halides in alkylation of bis(secondary) phosphines (RHP&sim;PHR). Enantiomerically pure P(Ph)(o-CF3CH2C6H 4)(CH2)2P(Ph)(o-CF3CH 2C6H4) was isolated.
520 $a Chapter Two. Mechanistic Investigations of Pt-Catalyzed Asymmetric Alkylation of Bis(secondary) Phosphines. Catalyst Editing and Cooperativity . The Pt-catalyzed alkylation of 1,3-bis(phenylphosphino)propane (1) with benzyl bromide gave 1,3-bis(benzylphenylphosphino)propane (2) with an er of 68+/-12 and a dr of 4.2+/-0.3. The selectivity was controlled by the catalyst, as shown by the synthesis and alkylation of PhHP(CH2)3P(Ph)(CH2Ph), which contained an enantiomerically enriched tertiary phosphine center. The major enantiomer was formed preferentially due to a catalyst editing process. A series of bis(secondary) phosphines PhHP(CH2)nPHPh (n = 2--6) was examined in the Pt-catalyzed alkylation with benzyl bromide. The distereoselectivity and enantioselectivity of alkylation depended on n, being greatest for n = 3 or 4 and least for n = 2.
520 $a Chapter Three. Enantioselective Synthesis of P-Stereogenic Benzophospholanes via Palladium-Catalyzed Intramolecular Cyclization. Enantioselective or diastereoselective intramolecular cyclization of functionalized secondary phosphines or their borane adducts catalyzed by chiral Pd(diphosphine) complexes gave P-stereogenic benzophospholanes in up to 70% ee. The chirality at phosphorus allowed for diastereoselective deprotonation/alkylation at the alpha-position. These results provide a new method for the synthesis of chiral phospholanes, which are valuable ligands in asymmetric catalysis.
520 $a Chapter Four. Enantioselective Synthesis of P-Stereogenic 1-Phosphaacenaphthaenes via Pt-Catalyzed Intramolecular Cyclization of Secondary Phosphines and Pt-Catalyzed Alkylation/Cyclization of Primary and Bis(primary) Phosphines. Pt-catalyzed tandem alkylation/cyclization of primary phosphines with 1-bromo-8-chloromethylnaphthalene yielded novel 1-phosphaacenaphthenes in enantioenriched form. Similar reactions with bis(primary)phosphines formed potential chelate ligands with diastereo- and enantioselectivity. Enantioselective cyclization of the functionalized secondary phosphine 1-bromo-8-phenylphosphinomethylnaphthalene catalyzed by chiral Pt(DuPhos)(Ar)(Cl) complexes gave Ph-AcePhos in up to 72% ee. These reactions, which appear to proceed via an unusual metal-mediated nucleophilic aromatic substitution pathway, yield a new class of heterocycles with potential applications in asymmetric catalysis.
520 $a Chapter Five. Synthesis, Structure, and Reactivity of Palladium Trans-stilbene Complexes, Catalyst Precursors with Novel Asymmetric Diphosphine Ligands. Novel catalyst precursors Pd(diphos*)(trans-stilbene) ( 2a-c, diphos* = PPF-t-Bu, CyPF-t-Bu, or BoPhoz) were prepared from the dichloride complexes Pd(diphos*)Cl2 (1a-c). These catalyst precursors reacted more quickly with PhI to yield Pd(diphos*)(Ph)(I) than the similar Pd(0) complexes Pd(diphos*)(dba). However, the stilbene complexes gave only racemic products in either inter- or intramolecular phosphination.
590 $a School code: 0059.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Organic. $3 516206
690 $a 0488
690 $a 0490
710 2 $a Dartmouth College. $b Chemistry. $3 1029796
773 0 $t Dissertation Abstracts International $g 69-10B.
790 $a 0059
790 1 0 $a BelBruno, Joseph $e committee member
790 1 0 $a Glueck, David S., $e advisor
790 1 0 $a Hughes, Russel P. $e committee member
790 1 0 $a Waterman, Rory $e committee member
791 $a Ph.D.
792 $a 2008
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3334062