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Rational design, synthesis, and solu...
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Giovannetti, Janet Susan.
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Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts.
Record Type:
Electronic resources : Monograph/item
Title/Author:
Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts./
Author:
Giovannetti, Janet Susan.
Description:
198 p.
Notes:
Source: Dissertation Abstracts International, Volume: 52-03, Section: B, page: 1423.
Contained By:
Dissertation Abstracts International52-03B.
Subject:
Chemistry, Inorganic. -
Online resource:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9122608
Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts.
Giovannetti, Janet Susan.
Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts.
- 198 p.
Source: Dissertation Abstracts International, Volume: 52-03, Section: B, page: 1423.
Thesis (Ph.D.)--University of Colorado at Boulder, 1990.
Catalytic asymmetric hydrogenation is an important technique for the synthesis of chiral compounds. The intimate mechanistic details are known for eneamide substrates. Structural features of catalyst intermediates and catalyst precursors in the solid state are also known. These mechanistic and structural features were exploited for the rational design of a new catalyst system. A new chiral bisphosphine, JANPAMP, was synthesized, characterized, and used as a ligand for asymmetric hydrogenation catalysts. JANPAMP has a remote functionality which is proposed to serve as a linkage between the substrate and the catalyst. Substrate binding and hydrogenation results for the JANPAMP catalyst were obtained to determine the selectivity of the catalyst. These results were compared to those for existing asymmetric hydrogenation catalyst systems.Subjects--Topical Terms:
517253
Chemistry, Inorganic.
Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts.
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Giovannetti, Janet Susan.
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Rational design, synthesis, and solution structure characterization of asymmetric hydrogenation catalysts.
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198 p.
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Source: Dissertation Abstracts International, Volume: 52-03, Section: B, page: 1423.
500
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Director: Clark Landis.
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Thesis (Ph.D.)--University of Colorado at Boulder, 1990.
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Catalytic asymmetric hydrogenation is an important technique for the synthesis of chiral compounds. The intimate mechanistic details are known for eneamide substrates. Structural features of catalyst intermediates and catalyst precursors in the solid state are also known. These mechanistic and structural features were exploited for the rational design of a new catalyst system. A new chiral bisphosphine, JANPAMP, was synthesized, characterized, and used as a ligand for asymmetric hydrogenation catalysts. JANPAMP has a remote functionality which is proposed to serve as a linkage between the substrate and the catalyst. Substrate binding and hydrogenation results for the JANPAMP catalyst were obtained to determine the selectivity of the catalyst. These results were compared to those for existing asymmetric hydrogenation catalyst systems.
520
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Structural features of the catalysts in solution are important for homogeneous catalysts. A new methodology for solution structure determination was developed using NMR techniques and using a viscous solvent for the measurements. Quantitative distance information was obtained using NOE mapping techniques and structural features were extracted from the solution NOE data using a new computational method, conformer population analysis. The NOE solution structures were compared with the crystal structures and molecular mechanics conformational analyses. The NOE data analysis reveals a truer picture than the solid state structures of the preferred conformations of these small molecules in solution. In principle, the origins of selectivity in solution may be determined using this solution structure determination methodology.
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School code: 0051.
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http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=9122608
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