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Catalytic Asymmetric Isomerizations of Alkynes To Allenes And Their Diastereoselective Functionalization Facilitated By An Organomanganese Auxiliary

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Date Issued:
2017
Summary:
The present dissertation research is largely focused on the methods to synthesize highly substituted allene derivatives from alkynes in conjugation with carbonyl-containing functional groups. A key aspect of this research involves methylcyclopentadienylmanganese dicarbonyl (MMD), an inexpensive and air-stable organometallic auxiliary linked to alkynyl carbonyls via an η2-bond. This auxiliary influences bond formation to achieve enhanced stereoselectivity without itself undergoing any chemical transformation. Chapter 1 accounts various examples of such transition metal auxiliaries including MMD. Typically conjugated alkynyl carbonyls do not isomerize to thermodynamically less favored allenes. However, with the MMD auxiliary in place, alkynyl carbonyl compounds undergo facile 1,3-proton shifts in the presence of a mild base to produce allene isomers. Although allenyl aldehydes are important building blocks, we note that direct methods to prepare them nonracemically are not known. Chapter 2 describes the development of a new cinchonine-based phase transfer catalyst to access non-racemic allenyl aldehydes from MMD-complexed alkynyl aldehydes. With the manganese auxiliary in place, nonracemic allenyl aldehydes were obtained in a weakly basic biphasic reaction system via enantioselective protonation conditions. Chapter 3 describes the second use of the MMD auxiliary to direct nucleophilic addition reactions to allenyl aldehydes for the preparation of 2,3-allenols diastereoselectively. In the absence of the MMD auxiliary, nucleophilic reactions to the carbonyl group of axially chiral allenyl aldehydes is poorly diastereoselective, which is a long-standing problem. We observed that, in addition to leading to non-racemic allenyl aldehydes, the MMD auxiliary could also be used to improve diastereoselectivity in carbonyl additions due to its proximal position on the 2,3-bond of the allenyl aldehyde. Chapter 4 describes the use of allenyl esters as metathesis quenching agents. It was observed that the addition of an allenyl ester after a metathesis reaction was complete; facilitate the removal of most ruthenium metal impurities using simple silica chromatographic purification.
Title: Catalytic Asymmetric Isomerizations of Alkynes To Allenes And Their Diastereoselective Functionalization Facilitated By An Organomanganese Auxiliary.
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Name(s): Roy, Animesh, author
Lepore, Salvatore D., Thesis advisor
Florida Atlantic University, Degree grantor
Charles E. Schmidt College of Science
Department of Chemistry and Biochemistry
Type of Resource: text
Genre: Electronic Thesis Or Dissertation
Date Created: 2017
Date Issued: 2017
Publisher: Florida Atlantic University
Place of Publication: Boca Raton, Fla.
Physical Form: application/pdf
Extent: 171 p.
Language(s): English
Summary: The present dissertation research is largely focused on the methods to synthesize highly substituted allene derivatives from alkynes in conjugation with carbonyl-containing functional groups. A key aspect of this research involves methylcyclopentadienylmanganese dicarbonyl (MMD), an inexpensive and air-stable organometallic auxiliary linked to alkynyl carbonyls via an η2-bond. This auxiliary influences bond formation to achieve enhanced stereoselectivity without itself undergoing any chemical transformation. Chapter 1 accounts various examples of such transition metal auxiliaries including MMD. Typically conjugated alkynyl carbonyls do not isomerize to thermodynamically less favored allenes. However, with the MMD auxiliary in place, alkynyl carbonyl compounds undergo facile 1,3-proton shifts in the presence of a mild base to produce allene isomers. Although allenyl aldehydes are important building blocks, we note that direct methods to prepare them nonracemically are not known. Chapter 2 describes the development of a new cinchonine-based phase transfer catalyst to access non-racemic allenyl aldehydes from MMD-complexed alkynyl aldehydes. With the manganese auxiliary in place, nonracemic allenyl aldehydes were obtained in a weakly basic biphasic reaction system via enantioselective protonation conditions. Chapter 3 describes the second use of the MMD auxiliary to direct nucleophilic addition reactions to allenyl aldehydes for the preparation of 2,3-allenols diastereoselectively. In the absence of the MMD auxiliary, nucleophilic reactions to the carbonyl group of axially chiral allenyl aldehydes is poorly diastereoselective, which is a long-standing problem. We observed that, in addition to leading to non-racemic allenyl aldehydes, the MMD auxiliary could also be used to improve diastereoselectivity in carbonyl additions due to its proximal position on the 2,3-bond of the allenyl aldehyde. Chapter 4 describes the use of allenyl esters as metathesis quenching agents. It was observed that the addition of an allenyl ester after a metathesis reaction was complete; facilitate the removal of most ruthenium metal impurities using simple silica chromatographic purification.
Identifier: FA00004918 (IID)
Degree granted: Dissertation (Ph.D.)--Florida Atlantic University, 2017.
Collection: FAU Electronic Theses and Dissertations Collection
Note(s): Includes bibliography.
Subject(s): Transition metal catalysts.
Stereochemistry.
Chemistry, Organic.
Chemistry, Physical and theoretical.
Asymmetric synthesis.
Held by: Florida Atlantic University Libraries
Sublocation: Digital Library
Persistent Link to This Record: http://purl.flvc.org/fau/fd/FA00004918
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Owner Institution: FAU
Is Part of Series: Florida Atlantic University Digital Library Collections.