자료유형  

 학위논문

Control Number  

0016931744

International Standard Book Number  

9798379613563

Dewey Decimal Classification Number  

547

Main Entry-Personal Name  

Forbes, Katherine Carmen.

Publication, Distribution, etc. (Imprint  

[S.l.] : Harvard University., 2023

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2023

Physical Description  

1 online resource(164 p.)

General Note  

Source: Dissertations Abstracts International, Volume: 84-12, Section: B.

General Note  

Advisor: Jacobsen, Eric N.

Dissertation Note  

Thesis (Ph.D.)--Harvard University, 2023.

Restrictions on Access Note  

This item must not be sold to any third party vendors.

Summary, Etc.  

요약In Chapter 1, we review organocatalytic approaches for the enantioselective synthesis of stereogenic-at-P(V) compounds. General organocatalytic activation modes used for constructing P(V) stereocenters are discussed, including covalent catalysis, hydrogen-bond-donor catalysis, and general base catalysis. Existing synthetic methods applying these modalities for the enantioselective synthesis of stereogenic-at-P(V) compounds are reviewed, and the proposed mechanisms for these reactions are discussed. In Chapter 2, we report the development of a hydrogen-bond-donor catalyzed desymmetrization of phosphonic dichlorides with amines to enantioselectively furnish chlorophosphonamidate building blocks using a commercially available catalyst. We demonstrate that chlorophosphonamidates possess two leaving groups which can be displaced sequentially and stereospecifically. Furthermore, we explore the use of chlorophosphonamidates as bifunctional stereogenic-at-P(V) building blocks which can serve as synthetic precursors to access a diverse array of stereogenic-at-P(V) targets. The synthetic utility of this methodology is established through its application to the synthesis of bioactive P-stereogenic targets. In Chapter 3, we detail the development of a hydrogen-bond-donor catalyzed desymmetrization of phosphinic acids via an enantioselective alkylation reaction with sulfonium reagents to generate chiral phosphinate esters. Evaluation of different sulfonium reagents revealed a significant effect of the sulfonium structure on enantioselectivity, with a thianthrene-derived sulfonium reagent yielding the phosphinate products with the highest levels of enantioenrichment. Moderate levels of enantioselectivity are observed with sterically hindered and unhindered phosphinic acids. 

Subject Added Entry-Topical Term  

Organic chemistry.

Subject Added Entry-Topical Term  

Physical chemistry.

Subject Added Entry-Topical Term  

Molecular chemistry.

Index Term-Uncontrolled  

Catalysis

Index Term-Uncontrolled  

Enantioselective synthesis

Index Term-Uncontrolled  

Phosphorus

Index Term-Uncontrolled  

P-stereogenic targets

Index Term-Uncontrolled  

Chlorophosphonamidates

Added Entry-Corporate Name  

Harvard University Chemistry and Chemical Biology

Host Item Entry  

Dissertations Abstracts International. 84-12B.

Host Item Entry  

Dissertation Abstract International

Electronic Location and Access  

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Control Number  

joongbu:639254