자료유형  

 학위논문

Control Number  

0017163778

International Standard Book Number  

9798342123235

Dewey Decimal Classification Number  

600

Main Entry-Personal Name  

Swann, William A.

Publication, Distribution, etc. (Imprint  

[S.l.] : Purdue University., 2024

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

354 p.

General Note  

Source: Dissertations Abstracts International, Volume: 86-04, Section: B.

General Note  

Advisor: Li, Christina W.;Bart, Suzanne Doucette;Marinero-Caceres, Ernesto;Wei, Alexander.

Dissertation Note  

Thesis (Ph.D.)--Purdue University, 2024.

Summary, Etc.  

요약Directed hydrogenation, in which product geometric selectivity is dictated by the binding of an ancillary directing group on the substrate to the catalyst, is typically achieved by homogeneous Rh and Ir complexes. No heterogeneous catalyst has been able to achieve equivalently high directivity due to a lack of control over substrate binding orientation at the catalyst surface. In this work, we demonstrate through structure-activity studies that careful control of surface ensemble geometry in bimetallic nanoparticle catalysts can confer hydroxyl-directed selectivity in heterogeneous double bond hydrogenation. We postulate that the oxophilic alloy component binds hydroxyl groups to pre-orient the molecule on the surface, while proximal noble metal atoms impart facially selective addition of hydride to the olefin. We found that controlling the degree of surface alloying between oxophilic and noble metal component as well as alloy component identity is critical to maximizing reaction selectivity and starting material conversion. Our optimized catalysts exhibit good functional group tolerance on a variety of cyclohexenol and cyclopentenol scaffolds, with Pd-Cu and Pt-Ni systems being developed for the diastereoselective hydrogenation of tri- and more challenging tetra-substituted olefins, respectively. The applicability of this method is then demonstrated in a four-step synthesis of a fine fragrance compound, (1R,2S)- (+)-cis-methyldihydrojasmonate (Paradisone®), with high yield and enantiopurity.

Subject Added Entry-Topical Term  

Hydrogen.

Subject Added Entry-Topical Term  

Alcohol.

Subject Added Entry-Topical Term  

Particle size.

Subject Added Entry-Topical Term  

Hydrogenation.

Subject Added Entry-Topical Term  

Catalysis.

Subject Added Entry-Topical Term  

Alloys.

Subject Added Entry-Topical Term  

Nanoparticles.

Subject Added Entry-Topical Term  

Natural products.

Subject Added Entry-Topical Term  

Solvents.

Subject Added Entry-Topical Term  

Adsorption.

Subject Added Entry-Topical Term  

Materials science.

Subject Added Entry-Topical Term  

Nanotechnology.

Subject Added Entry-Topical Term  

Organic chemistry.

Added Entry-Corporate Name  

Purdue University.

Host Item Entry  

Dissertations Abstracts International. 86-04B.

Electronic Location and Access  

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Control Number  

joongbu:658329