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Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides

Record Type:	Electronic resources : Monograph/item
Title/Author:	Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides
Author:	Sammis, Glenn M.
Description:	138 p.
Notes:	Adviser: Eric N. Jacobsen.
Notes:	Source: Dissertation Abstracts International, Volume: 65-05, Section: B, page: 2425.
Contained By:	Dissertation Abstracts International65-05B.
Subject:	Chemistry, Organic.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3131978
ISBN:	0496792180

Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides
Sammis, Glenn M.

Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides [electronic resource] - 138 p.

Adviser: Eric N. Jacobsen.

Thesis (Ph.D.)--Harvard University, 2004.

*Please refer to dissertation for diagrams.

ISBN: 0496792180Subjects--Topical Terms:

193634
Chemistry, Organic.

Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides
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245 1 0 $a Development of homobimetallic and heterobimetallic catalysts for the enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides $h [electronic resource]
300 $a 138 p.
500 $a Adviser: Eric N. Jacobsen.
500 $a Source: Dissertation Abstracts International, Volume: 65-05, Section: B, page: 2425.
502 $a Thesis (Ph.D.)--Harvard University, 2004.
520 # $a *Please refer to dissertation for diagrams.
520 # $a I. Development of a homobimetallic catalyzed enantioselective conjugate addition of cyanide to alpha,beta-unsaturated imides. (Salen)Al-Cl complex 1a catalyzes the asymmetric conjugate addition of hydrogen cyanide to alpha,beta-unsaturated imides in high yields and enantioselectivities. The cyanide adducts are readily converted into a variety useful chiral building blocks, including alpha-substituted-beta-amino acids and beta-substituted-gamma-aminobutyric acids. A second-order dependence on catalyst concentration and a positive non-linear correlation of catalyst ee to product ee suggest a cooperative bimetallic mechanism involving both nucleophile and electrophile activation.*
520 # $a II. Cooperative heterobimetallic catalysis: Application to the highly enantioselective conjugate addition of cyanide to alpha,beta- unsaturated imides. Cooperative heterobimetallic catalysis was used as a design principle to improve the reactivity of the homobimetallic conjugate addition of hydrogen cyanide to alpha,beta-unsaturated imides. A dual catalyst pathway involving (salen) aluminum chloride complex 1a and (i-propyl pybox) erbium chloride complex 4 provides measurable improvements in the rates and enantioselectivities relative to complex 1a alone. Mechanistic studies indicate the presence of competing heterobimetallic and homobimetallic pathways.
520 # $a To develop a system that operates by a purely heterobimetallic mechanism, each catalyst was optimized for single-component activation. A second-generation dual catalyst system involving a mu-oxo (salen) aluminum complex 1b and (i-propyl pybox) erbium chloride complex 4 provides a significant improvement relative to both the homobimetallic and the first generation dual catalyst systems. Mechanistic investigations indicate that the reaction proceeds through a heterobimetallic pathway, presumably one in which a mu-oxo (salen) aluminum complex 1b activates the imide and (i-propyl pybox) erbium chloride complex 4 activates hydrogen cyanide.*
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790 1 0 $a Jacobsen, Eric N., $e advisor
791 $a Ph.D.
792 $a 2004
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