I. Palladium-catalyzed anti-Markovnikov oxidative amination of olefins II. Catalytic deracemization of axially chiral diols III. Three component carboamination of electron deficient alkenes

Kohler, Daniel Gregory

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Description

Title

I. Palladium-catalyzed anti-Markovnikov oxidative amination of olefins II. Catalytic deracemization of axially chiral diols III. Three component carboamination of electron deficient alkenes

Author(s)

Kohler, Daniel Gregory

Issue Date

2018-11-29

Director of Research (if dissertation) or Advisor (if thesis)

Hull, Kami L.

Doctoral Committee Chair(s)

Hull, Kami L.

Committee Member(s)

• Fout, Alison R.
• Moore, Jeffrey S.
• Zimmerman, Steven C.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Organic Synthesis
• Methodology
• Catalysis
• Amination
• Oxidation

Abstract

Organic synthesis is the backbone of global chemical production. Agrochemicals, pharmaceuticals, materials, and fine chemicals are all accessed by organic synthesis, so the development of new methods in organic chemistry is a critical area of research for an efficient and effective chemical industry. Specifically, methods which are able to construct new C–X bonds in few steps, selectively, and with a minimum of chemical waste are highly sought after, as many such methods rely on functional group conversions which are often step- and atom-inefficient, or are extremely limited in scope. A powerful strategy to achieve the outlined goals is the use of transition-metal catalysis, whereby otherwise difficult or impossible transformations such as the mild functionalization of readily available and inert alkenes can be enabled without the use of stoichiometric additives or activating reagents. In this thesis will be described the development of such methods intended to address some these problems. First we have developed a palladium-catalyzed anti-Markovnikov oxidative amination of unactivated alkenes. This transformation allows for the generation of primary C–N bonds by coupling the terminus of a C–C double bond with an acidic nitrogen nucleophile such as phthalimide. As the terminal oxidant is molecular oxygen, the only byproduct is half an equivalent of water, rendering the reaction very environmentally friendly. The reaction requires a functional group distal to the alkene to facilitate the reaction, but the nature of this functional group can be varied greatly, including aryl, alkoxy, amide, and imide groups. The mechanism of the reaction has been studied extensively, and it was shown that the use of an in situ generated palladate catalyst proved essential to achieve the unusual regioselectivity observed compared to related oxidative amination reactions. Next we have developed a copper-catalyzed 3-component carboamination reaction. This transformation converts alkenes, aryl amines, and alkyl halides into densely functionalized lactams. The use of acrylate alkenes is a notable step forward in the area of radical carboamination, as previous work has largely been limited to very electron rich alkenes such as substituted styrene. This reaction was found to be fairly tolerant of substitution on the amine as well as the identity of the conjugated alkene, working very well on acrylates and acrylamides of varying identities. Finally, we have shown a copper-catalyzed deracemization of 2,2’-BINOL. Discovery of a catalyst capable of racemizing BINOL under mild conditions, combined with a resolving agent such as a cinchonidinium salt capable of sequestering a single desired enantiomer, creates a system that can convert any enantiomeric mixture of substrate into an enantiopure sample. The scope of the racemization was found to be fairly broad, with the catalyst capable of converting a wide array of axially chiral aryl diols into racemic samples including 3,3’- and 6,6’-substituted derivatives of BINOL with varying steric and electronic properties. Development of this work is ongoing in our lab, with identification of general resolution agents and more active catalysts being explored.

Graduation Semester

2018-12

Type of Resource

text

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http://hdl.handle.net/2142/102919

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© 2018 DANIEL GREGORY KOHLER

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