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Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis./
作者:	Forbes, Katherine Carmen.
面頁冊數:	1 online resource (164 pages)
附註:	Source: Dissertations Abstracts International, Volume: 84-12, Section: B.
Contained By:	Dissertations Abstracts International84-12B.
標題:	Organic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30421697click for full text (PQDT)
ISBN:	9798379613563

Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis.
Forbes, Katherine Carmen.

Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis. - 1 online resource (164 pages)

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

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

Includes bibliographical references

In 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.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9798379613563Subjects--Topical Terms:

523952
Organic chemistry.
Subjects--Index Terms:

CatalysisIndex Terms--Genre/Form:

542853
Electronic books.

Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis.
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