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Development of a Ni-Catalyzed Enantioselective Intramolecular Mizoroki-Heck Reaction for the Synthesis of Phenanthridinone Derivatives.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Development of a Ni-Catalyzed Enantioselective Intramolecular Mizoroki-Heck Reaction for the Synthesis of Phenanthridinone Derivatives./
Author:	Rachii, Diana.
Description:	1 online resource (402 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 85-11, Section: B.
Contained By:	Dissertations Abstracts International85-11B.
Subject:	Chemistry. -
Online resource:	click for full text (PQDT)
ISBN:	9798382718729

Development of a Ni-Catalyzed Enantioselective Intramolecular Mizoroki-Heck Reaction for the Synthesis of Phenanthridinone Derivatives.
Rachii, Diana.

Development of a Ni-Catalyzed Enantioselective Intramolecular Mizoroki-Heck Reaction for the Synthesis of Phenanthridinone Derivatives. - 1 online resource (402 pages)

Source: Dissertations Abstracts International, Volume: 85-11, Section: B.

Thesis (Ph.D.)--Bryn Mawr College, 2024.

Includes bibliographical references

The Birch reduction-alkylation coupled to the desymmetrizing Mizoroki-Heck reaction is a novel synthetic tool to form potentially bioactive phenanthridinone analogs from inexpensive and easily available starting materials. This work describes a rare example of the direct replacement of palladium for nickel in our previously reported enantioselective intramolecular Heck reaction. A Ni-catalyzed enantioselective intramolecular Mizoroki-Heck reaction has been developed to transform symmetrical 1,4-cyclohexadienes with attached aryl halides to phenanthridinone analogs containing quaternary stereocenters. Moreover, this approach provides direct access to six-member ring heterocyclic systems bearing all-carbon quaternary stereocenters, which have been much more challenging to form enantioselectively with nickel-catalyzed Heck reactions. The first part of this project describes important advances in reaction optimization enabling control of unwanted proto-dehalogenation and alkene reduction side products. The second section focuses on the development of enantioselective strategy with a newly synthesized chiral iQuinox-type bidentate ligand. In the third section, we describe efforts to explore the substrate scope and to subsequently transform the 1,3-diene Heck products into molecules with potentially greater therapeutic relevance. In the last project chapter, mechanistic investigations and a computational study of the key 1,2-migratory insertionstep shed light on the catalytic cycle and the basis for the enantioselectivity. Altogether, this work presents a very attractive alternative to the palladium-catalyzed process and should facilitate the application of Ni catalysis to traditional Heck transformations.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798382718729Subjects--Topical Terms:

593913
Chemistry.
Subjects--Index Terms:

Heck reactionIndex Terms--Genre/Form:

554714
Electronic books.

Development of a Ni-Catalyzed Enantioselective Intramolecular Mizoroki-Heck Reaction for the Synthesis of Phenanthridinone Derivatives.
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520 $a The Birch reduction-alkylation coupled to the desymmetrizing Mizoroki-Heck reaction is a novel synthetic tool to form potentially bioactive phenanthridinone analogs from inexpensive and easily available starting materials. This work describes a rare example of the direct replacement of palladium for nickel in our previously reported enantioselective intramolecular Heck reaction. A Ni-catalyzed enantioselective intramolecular Mizoroki-Heck reaction has been developed to transform symmetrical 1,4-cyclohexadienes with attached aryl halides to phenanthridinone analogs containing quaternary stereocenters. Moreover, this approach provides direct access to six-member ring heterocyclic systems bearing all-carbon quaternary stereocenters, which have been much more challenging to form enantioselectively with nickel-catalyzed Heck reactions. The first part of this project describes important advances in reaction optimization enabling control of unwanted proto-dehalogenation and alkene reduction side products. The second section focuses on the development of enantioselective strategy with a newly synthesized chiral iQuinox-type bidentate ligand. In the third section, we describe efforts to explore the substrate scope and to subsequently transform the 1,3-diene Heck products into molecules with potentially greater therapeutic relevance. In the last project chapter, mechanistic investigations and a computational study of the key 1,2-migratory insertionstep shed light on the catalytic cycle and the basis for the enantioselectivity. Altogether, this work presents a very attractive alternative to the palladium-catalyzed process and should facilitate the application of Ni catalysis to traditional Heck transformations.
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