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Mechanistic studies of manganese(sal...

Pospisil, Paul Joseph.

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Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations./
Author:	Pospisil, Paul Joseph.
Description:	242 p.
Notes:	Source: Dissertation Abstracts International, Volume: 57-02, Section: B, page: 1091.
Contained By:	Dissertation Abstracts International57-02B.
Subject:	Chemistry, Organic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9619546

Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations.
Pospisil, Paul Joseph.

Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations. - 242 p.

Source: Dissertation Abstracts International, Volume: 57-02, Section: B, page: 1091.

Thesis (Ph.D.)--Harvard University, 1996.

The mechanism of Mn(salen) catalyzed asymmetric oxidation reactions was investigated. Specifically, the asymmetric epoxidation, sulfoxidation, and kinetic resolution via C-H activation catalyzed by chiral Mn(III)(salen) complexes (1) were examined with several terminal oxidants.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)Subjects--Topical Terms:

516206
Chemistry, Organic.

Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations.
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100 1 $a Pospisil, Paul Joseph. $3 1903228
245 1 0 $a Mechanistic studies of manganese(salen) catalyzed asymmetric oxidations.
300 $a 242 p.
500 $a Source: Dissertation Abstracts International, Volume: 57-02, Section: B, page: 1091.
502 $a Thesis (Ph.D.)--Harvard University, 1996.
520 $a The mechanism of Mn(salen) catalyzed asymmetric oxidation reactions was investigated. Specifically, the asymmetric epoxidation, sulfoxidation, and kinetic resolution via C-H activation catalyzed by chiral Mn(III)(salen) complexes (1) were examined with several terminal oxidants.(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)
520 $a Using stereochemical results, kinetic studies, isolation of possible intermediates, and isotope effect experiments, a detailed description of the catalytic cycle has emerged. The Mn(salen) catalyzed oxidations proceed through a multi-step process involving a high valent Mn(V)(salen)oxo. The detection of multiple selective and unselective oxidation pathways for various terminal oxidants has provided a better understanding of variables that affect selective oxidations.
520 $a The pronounced effect that additives, such as amine N-oxide derivatives have on increasing epoxidation rates, catalyst turnovers, and stereoselectivities was also addressed mechanistically. The remarkable role of tetraalkylammonium salt additives, in biasing trans epoxide formation in the epoxidation of cis alkenes was also studied. The amine N-oxide additives were shown to act as axial ligands and to induce ligand accelerated catalysis.
520 $a X-Ray structural studies of several highly enantioselective Mn(salen) epoxidation catalysts suggested the existence of rigid and flexible domains in these complexes. A stereochemical model for the epoxidation of olefins was constructed based on the conformational properties of the catalyst in the solid state and results from the asymmetric oxidation of model substrates with catalysts with varying steric properties.
590 $a School code: 0084.
650 4 $a Chemistry, Organic. $3 516206
650 4 $a Chemistry, Inorganic. $3 517253
690 $a 0490
690 $a 0488
710 2 0 $a Harvard University. $3 528741
773 0 $t Dissertation Abstracts International $g 57-02B.
790 $a 0084
791 $a Ph.D.
792 $a 1996
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9619546