Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis- [electronic resource]
Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis- [electronic resource]
- 자료유형
- 학위논문파일 국외
- 최종처리일시
- 20240214100112
- ISBN
- 9798379613563
- DDC
- 547
- 서명/저자
- Enantioselective Synthesis of Stereogenic-At-Phosphorus(V) Compounds via Hydrogen-Bond-Donor Catalysis - [electronic resource]
- 발행사항
- [S.l.]: : Harvard University., 2023
- 발행사항
- Ann Arbor : : ProQuest Dissertations & Theses,, 2023
- 형태사항
- 1 online resource(164 p.)
- 주기사항
- Source: Dissertations Abstracts International, Volume: 84-12, Section: B.
- 주기사항
- Advisor: Jacobsen, Eric N.
- 학위논문주기
- Thesis (Ph.D.)--Harvard University, 2023.
- 사용제한주기
- This item must not be sold to any third party vendors.
- 초록/해제
- 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.
- 일반주제명
- Organic chemistry.
- 일반주제명
- Physical chemistry.
- 일반주제명
- Molecular chemistry.
- 키워드
- Catalysis
- 키워드
- Phosphorus
- 기타저자
- Harvard University Chemistry and Chemical Biology
- 기본자료저록
- Dissertations Abstracts International. 84-12B.
- 기본자료저록
- Dissertation Abstract International
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.