東華大學圖書館 |

Language: English

Help

回圖書館首頁

手機版館藏查詢

Back

Switch To: Labeled | MARC Mode | ISBD

Linked to FindBook

Google Book

Amazon

博客來

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

Record Type:	Electronic resources : Monograph/item
Title/Author:	Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis./
Author:	Forbes, Katherine Carmen.
Description:	1 online resource (164 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 84-12, Section: B.
Contained By:	Dissertations Abstracts International84-12B.
Subject:	Organic chemistry. -
Online resource:	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.
LDR:03201nmm a2200397K 4500 001 2362998
005 20231109104728.5
006 m o d
007 cr mn ---uuuuu
008 241011s2023 xx obm 000 0 eng d
020 $a 9798379613563
035 $a (MiAaPQ)AAI30421697
035 $a AAI30421697
040 $a MiAaPQ $b eng $c MiAaPQ $d NTU
100 1 $a Forbes, Katherine Carmen. $3 3703741
245 1 0 $a Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis.
264 0 $c 2023
300 $a 1 online resource (164 pages)
336 $a text $b txt $2 rdacontent
337 $a computer $b c $2 rdamedia
338 $a online resource $b cr $2 rdacarrier
500 $a Source: Dissertations Abstracts International, Volume: 84-12, Section: B.
500 $a Advisor: Jacobsen, Eric N.
502 $a Thesis (Ph.D.)--Harvard University, 2023.
504 $a Includes bibliographical references
520 $a 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.
533 $a Electronic reproduction. $b Ann Arbor, Mich. : $c ProQuest, $d 2023
538 $a Mode of access: World Wide Web
650 4 $a Organic chemistry. $3 523952
650 4 $a Physical chemistry. $3 1981412
650 4 $a Molecular chemistry. $3 1071612
653 $a Catalysis
653 $a Enantioselective synthesis
653 $a Phosphorus
653 $a P-stereogenic targets
653 $a Chlorophosphonamidates
655 7 $a Electronic books. $2 lcsh $3 542853
690 $a 0490
690 $a 0431
690 $a 0494
710 2 $a ProQuest Information and Learning Co. $3 783688
710 2 $a Harvard University. $b Chemistry and Chemical Biology. $3 2094763
773 0 $t Dissertations Abstracts International $g 84-12B.
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30421697 $z click for full text (PQDT)