ingest
cdrApp
2017-07-06T11:50:01.705Z
082b3de9-6030-4a3e-a983-035a47fc699e
modifyDatastreamByValue
RELS-EXT
fedoraAdmin
2017-07-06T11:59:18.165Z
Setting exclusive relation
modifyDatastreamByValue
RELS-EXT
fedoraAdmin
2017-07-06T11:59:26.411Z
Setting exclusive relation
addDatastream
MD_TECHNICAL
fedoraAdmin
2017-07-06T11:59:34.517Z
Adding technical metadata derived by FITS
modifyDatastreamByValue
RELS-EXT
fedoraAdmin
2017-07-06T11:59:50.799Z
Setting exclusive relation
addDatastream
MD_FULL_TEXT
fedoraAdmin
2017-07-06T11:59:59.941Z
Adding full text metadata extracted by Apache Tika
modifyDatastreamByValue
RELS-EXT
fedoraAdmin
2017-07-06T12:00:19.489Z
Setting exclusive relation
modifyDatastreamByValue
RELS-EXT
cdrApp
2017-07-06T12:27:45.067Z
Setting exclusive relation
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-01-25T11:46:00.727Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-01-27T11:56:41.721Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-03-14T08:53:29.085Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-05-17T20:27:03.785Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-07-11T07:26:12.535Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-07-18T03:36:04.422Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-08-16T16:45:38.990Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-09-27T03:17:55.254Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2018-10-12T03:45:13.866Z
modifyDatastreamByValue
MD_DESCRIPTIVE
cdrApp
2019-03-21T13:23:54.206Z
Alexander
Venning
Author
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles
An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis.
II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation
A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates.
III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling
A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
Spring 2017
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated
Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the
application of alkyl electrophiles in cross-coupling reactions is presented, highlighting
the importance of this reactivity and challenges associated therein. Recent advances in
alkyl cross-coupling are discussed, from both a process development and mechanistic
perspective, to describe the current state of the field. Advances in hybrid
organometallic-radical reactivity are also considered, with particular focus on its
application in alkyl cross-coupling and perspective on mechanistic analysis. II.
Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed,
intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This
process is successful with both iodides and bromides, including those with β-hydrogen
atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as
well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays
compatibility with a diverse range of functional groups, including those which are base-
or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the
presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to
Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl
halides with alkenes is presented. Reaction conditions determine whether the end product
retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction,
or if the alkene component is restored, affecting a formal Heck-type transformation. The
manifold is capable of performing both transformations with unactivated alkyl bromides and
a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also
enables formation of both 5- and 6-membered rings. A mechanistic investigation of this
reaction is presented, which suggests the operation of a catalytic, hybrid
organometallic-radical process.
Spring 2017
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic,
Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting
institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
Spring 2017
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017-05
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
2017-05
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
2017-05
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagné
Thesis advisor
text
2017-05
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagne
Thesis advisor
text
2017-05
University of North Carolina at Chapel Hill
Degree granting institution
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis; Cross-Coupling; Organometallic; Palladium
eng
Doctor of Philosophy
Dissertation
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagne
Thesis advisor
text
2017-05
University of North Carolina at Chapel Hill
Degree granting institution
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis, Cross-Coupling, Organometallic, Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Chemistry
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagne
Thesis advisor
text
2017-05
Alexander
Venning
Creator
Department of Chemistry
College of Arts and Sciences
Palladium-Catalyzed Carbon-Carbon Bond-Forming Reactions with Unactivated Alkyl Electrophiles
I. Cross-Coupling Reactions with Alkyl Electrophiles An overview of the application of alkyl electrophiles in cross-coupling reactions is presented, highlighting the importance of this reactivity and challenges associated therein. Recent advances in alkyl cross-coupling are discussed, from both a process development and mechanistic perspective, to describe the current state of the field. Advances in hybrid organometallic-radical reactivity are also considered, with particular focus on its application in alkyl cross-coupling and perspective on mechanistic analysis. II. Palladium-Catalyzed Ring-Forming Aromatic C-H Alkylation A palladium-catalyzed, intramolecular aromatic C-H alkylation with unactivated alkyl halides is described. This process is successful with both iodides and bromides, including those with β-hydrogen atoms present. It also tolerates both electron-rich and electron-poor aromatic rings, as well as heteroaromatic substrates. The mild, palladium-catalyzed approach displays compatibility with a diverse range of functional groups, including those which are base- or nucleophile-sensitive. A mechanistic investigation is also presented, suggesting the presence of radical intermediates. III. A Versatile, Palladium-Catalyzed Approach to Alkene-Alkyl Halide Coupling A method for the palladium-catalyzed coupling of alkyl halides with alkenes is presented. Reaction conditions determine whether the end product retains the alkyl halide moiety in an atom-transfer radical cyclization (ATRC) reaction, or if the alkene component is restored, affecting a formal Heck-type transformation. The manifold is capable of performing both transformations with unactivated alkyl bromides and a variety of terminal, di- and tri-substituted alkenes under argon atmosphere. It also enables formation of both 5- and 6-membered rings. A mechanistic investigation of this reaction is presented, which suggests the operation of a catalytic, hybrid organometallic-radical process.
2017
Chemistry
Organic chemistry
Catalysis; Cross-Coupling; Organometallic; Palladium
eng
Doctor of Philosophy
Dissertation
University of North Carolina at Chapel Hill Graduate School
Degree granting institution
Erik
Alexanian
Thesis advisor
David
Nicewicz
Thesis advisor
Jeffrey
Aubé
Thesis advisor
Alexander
Miller
Thesis advisor
Michel
Gagne
Thesis advisor
text
2017-05
Venning_unc_0153D_16925.pdf
uuid:2d8a3917-a303-4420-af17-8cf9e3faefcb
proquest
2017-04-17T22:05:14Z
2019-07-06T00:00:00
application/pdf
29910109
yes