{"id":{"repo_id":"duke","oai_identifier":"oai:dukespace.lib.duke.edu:10161/5533"},"canonical_url":"https://search.dev.ndltd.org/etd/duke/oai:dukespace.lib.duke.edu:10161/5533","repository":{"repo_id":"duke","name":"Duke University","base_url":"https://dukespace.lib.duke.edu/server/oai/request"},"display":{"title":"Gold(I) and Platinum(II)-Catalyzed Hydrofunctionalization of Allenes and Alkenes with Carbon and Nitrogen Nucleophiles","abstract":"<p><p>The wide-spread occurrence of biologically active nitrogen-containing heterocycles and allylic amines inspired us to develop atom-economical methods for their syntheses.</p></p><p><p>A cationic gold(I) <italic>N</italic>-heterocyclic carbene complex catalyzed the intermolecular hydroarylation of allenes with indoles to form (<italic>E</italic>)-allylic indoles in modest to good yield at room temperature. The protocol was effective for monosubstituted, 1,3-disubstituted, and tetrasubstituted allenes and various indoles.</p> </p><p><p>Platinum(II) bis(phosphine) complexes catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines in good yield with selective formation of (<italic>E</italic>)-allylic amines. The scope of the protocol included aryl and alkyl monosubstituted allenes as well as a variety of both cyclic and acyclic secondary alkylamines.</p></p><p><p>The scope of gold(I)-catalyzed intermolecular hydroamination of 1-alkenes with 1-methyl-2-imidazolidinone was expanded to include additional 1-alkenes functionalized with carboxylic acid derivatives. However, a nucleophile screen failed to identify nucleophiles other than cyclic ureas and 2-oxazolidinone that efficiently undergo hydroamination with 1-alkenes. Various carbamates, arylamines, amide derivatives, sulfur-containing amide derivatives, and &alpha;-heteroatom compounds failed to react with 1-octene under gold(I)-catalyzed conditions.</p></p><p><p>A chiral bis(gold) phosphine complex catalyzed the stereoconvergent, intermolecular enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with carbamates to form <italic>N</italic>-allylic carbamates in good to high yield with up to 92% <italic>ee</italic>. In addition, enantiopurity experiments suggested the nature of the catalytically active species changes with increasing concentration of <italic>N</italic>-allylic carbamate.</p></p>","abstract_html":"&lt;p&gt;&lt;p&gt;The wide-spread occurrence of biologically active nitrogen-containing heterocycles and allylic amines inspired us to develop atom-economical methods for their syntheses.&lt;/p&gt;&lt;/p&gt;&lt;p&gt;&lt;p&gt;A cationic gold(I) &lt;italic&gt;N&lt;/italic&gt;-heterocyclic carbene complex catalyzed the intermolecular hydroarylation of allenes with indoles to form (&lt;italic&gt;E&lt;/italic&gt;)-allylic indoles in modest to good yield at room temperature. The protocol was effective for monosubstituted, 1,3-disubstituted, and tetrasubstituted allenes and various indoles.&lt;/p&gt; &lt;/p&gt;&lt;p&gt;&lt;p&gt;Platinum(II) bis(phosphine) complexes catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines in good yield with selective formation of (&lt;italic&gt;E&lt;/italic&gt;)-allylic amines. The scope of the protocol included aryl and alkyl monosubstituted allenes as well as a variety of both cyclic and acyclic secondary alkylamines.&lt;/p&gt;&lt;/p&gt;&lt;p&gt;&lt;p&gt;The scope of gold(I)-catalyzed intermolecular hydroamination of 1-alkenes with 1-methyl-2-imidazolidinone was expanded to include additional 1-alkenes functionalized with carboxylic acid derivatives. However, a nucleophile screen failed to identify nucleophiles other than cyclic ureas and 2-oxazolidinone that efficiently undergo hydroamination with 1-alkenes. Various carbamates, arylamines, amide derivatives, sulfur-containing amide derivatives, and &amp;alpha;-heteroatom compounds failed to react with 1-octene under gold(I)-catalyzed conditions.&lt;/p&gt;&lt;/p&gt;&lt;p&gt;&lt;p&gt;A chiral bis(gold) phosphine complex catalyzed the stereoconvergent, intermolecular enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with carbamates to form &lt;italic&gt;N&lt;/italic&gt;-allylic carbamates in good to high yield with up to 92% &lt;italic&gt;ee&lt;/italic&gt;. In addition, enantiopurity experiments suggested the nature of the catalytically active species changes with increasing concentration of &lt;italic&gt;N&lt;/italic&gt;-allylic carbamate.&lt;/p&gt;&lt;/p&gt;","abstract_has_math":false,"creators":["Butler, Kristina LeAnne"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Widenhoefer, Ross A"],"committee_chairs":[],"committee_members":[],"year":2012,"date_issued":"2012","date_published":"2012","updated_at":"2026-07-24T02:07:05Z","subjects":["Chemistry","allene","gold(I)","hydroamination","hydroarylation","platinum(II)"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10161/5533","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Widenhoefer, Ross A"]},{"key":"dc:creator","label":"Author","values":["Butler, Kristina LeAnne"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2012-05-25T20:18:11Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2014-05-15T04:30:05Z"]},{"key":"dc:date.issued","label":"Date","values":["2012"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","allene","gold(I)","hydroamination","hydroarylation","platinum(II)"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10161/5533"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["<p><p>The wide-spread occurrence of biologically active nitrogen-containing heterocycles and allylic amines inspired us to develop atom-economical methods for their syntheses.</p></p><p><p>A cationic gold(I) <italic>N</italic>-heterocyclic carbene complex catalyzed the intermolecular hydroarylation of allenes with indoles to form (<italic>E</italic>)-allylic indoles in modest to good yield at room temperature. The protocol was effective for monosubstituted, 1,3-disubstituted, and tetrasubstituted allenes and various indoles.</p> </p><p><p>Platinum(II) bis(phosphine) complexes catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines in good yield with selective formation of (<italic>E</italic>)-allylic amines. The scope of the protocol included aryl and alkyl monosubstituted allenes as well as a variety of both cyclic and acyclic secondary alkylamines.</p></p><p><p>The scope of gold(I)-catalyzed intermolecular hydroamination of 1-alkenes with 1-methyl-2-imidazolidinone was expanded to include additional 1-alkenes functionalized with carboxylic acid derivatives. However, a nucleophile screen failed to identify nucleophiles other than cyclic ureas and 2-oxazolidinone that efficiently undergo hydroamination with 1-alkenes. Various carbamates, arylamines, amide derivatives, sulfur-containing amide derivatives, and &alpha;-heteroatom compounds failed to react with 1-octene under gold(I)-catalyzed conditions.</p></p><p><p>A chiral bis(gold) phosphine complex catalyzed the stereoconvergent, intermolecular enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with carbamates to form <italic>N</italic>-allylic carbamates in good to high yield with up to 92% <italic>ee</italic>. In addition, enantiopurity experiments suggested the nature of the catalytically active species changes with increasing concentration of <italic>N</italic>-allylic carbamate.</p></p>"]},{"key":"dc:title","label":"Title","values":["Gold(I) and Platinum(II)-Catalyzed Hydrofunctionalization of Allenes and Alkenes with Carbon and Nitrogen Nucleophiles"]}]}],"canonical_facts":{"dc:contributor.advisor":["Widenhoefer, Ross A"],"dc:creator":["Butler, Kristina LeAnne"],"dc:date.accessioned":["2012-05-25T20:18:11Z"],"dc:date.available":["2014-05-15T04:30:05Z"],"dc:date.issued":["2012"],"dc:description.abstract":["<p><p>The wide-spread occurrence of biologically active nitrogen-containing heterocycles and allylic amines inspired us to develop atom-economical methods for their syntheses.</p></p><p><p>A cationic gold(I) <italic>N</italic>-heterocyclic carbene complex catalyzed the intermolecular hydroarylation of allenes with indoles to form (<italic>E</italic>)-allylic indoles in modest to good yield at room temperature. The protocol was effective for monosubstituted, 1,3-disubstituted, and tetrasubstituted allenes and various indoles.</p> </p><p><p>Platinum(II) bis(phosphine) complexes catalyzed the intermolecular hydroamination of monosubstituted allenes with secondary alkylamines in good yield with selective formation of (<italic>E</italic>)-allylic amines. The scope of the protocol included aryl and alkyl monosubstituted allenes as well as a variety of both cyclic and acyclic secondary alkylamines.</p></p><p><p>The scope of gold(I)-catalyzed intermolecular hydroamination of 1-alkenes with 1-methyl-2-imidazolidinone was expanded to include additional 1-alkenes functionalized with carboxylic acid derivatives. However, a nucleophile screen failed to identify nucleophiles other than cyclic ureas and 2-oxazolidinone that efficiently undergo hydroamination with 1-alkenes. Various carbamates, arylamines, amide derivatives, sulfur-containing amide derivatives, and &alpha;-heteroatom compounds failed to react with 1-octene under gold(I)-catalyzed conditions.</p></p><p><p>A chiral bis(gold) phosphine complex catalyzed the stereoconvergent, intermolecular enantioselective hydroamination of chiral, racemic 1,3-disubstituted allenes with carbamates to form <italic>N</italic>-allylic carbamates in good to high yield with up to 92% <italic>ee</italic>. In addition, enantiopurity experiments suggested the nature of the catalytically active species changes with increasing concentration of <italic>N</italic>-allylic carbamate.</p></p>"],"dc:identifier.uri":["https://hdl.handle.net/10161/5533"],"dc:subject":["Chemistry","allene","gold(I)","hydroamination","hydroarylation","platinum(II)"],"dc:title":["Gold(I) and Platinum(II)-Catalyzed Hydrofunctionalization of Allenes and Alkenes with Carbon and Nitrogen Nucleophiles"],"dc:type":["Dissertation"]},"updated_at":"2026-07-24T02:07:05Z"}