Cascade reactions, also referred to as domino reactions, have been widely used for the formation of carbon-carbon bonds. This type of reaction has the potential to circumvent protection and deprotection steps, shortening an overall synthetic process.
The Morita-Baylis-Hillman (MBH) reaction is a particularly notable example of an anionic domino reaction which provides straightforward access to β'-hydroxy-α,β-unsaturated carbonyl compounds from aldehydes and α,β-unsaturated carbonyls. However, despite the importance of the Baylis-Hillman reaction, it is slow, reaction yields are quite low, and the process is not general, as it rarely works for β-substituted α,β-unsaturated carbonyl species. Herein, we report an alternative approach to the preparation of MBH adducts employing an anti-selective direct aldol cascade reaction followed by oxidative elimination. This alternative process is rapid, efficient, and generally applicable, even to β-substituted α,β-unsaturated compounds.
Progress toward the asymmetric total synthesis of apratoxin D is described. The key step of the synthesis is the asymmetric α,α-bisalkylation of chiral N-amino cyclic carbamate (ACC) hydrazones, a new methodology developed by our group. Herein we demonstrate the utility of this method for convergent total syntheses.
","abstract_html":"<p>Cascade reactions, also referred to as domino reactions, have been widely used for the formation of carbon-carbon bonds. This type of reaction has the potential to circumvent protection and deprotection steps, shortening an overall synthetic process.</p><p>The Morita-Baylis-Hillman (MBH) reaction is a particularly notable example of an anionic domino reaction which provides straightforward access to β'-hydroxy-α,β-unsaturated carbonyl compounds from aldehydes and α,β-unsaturated carbonyls. However, despite the importance of the Baylis-Hillman reaction, it is slow, reaction yields are quite low, and the process is not general, as it rarely works for β-substituted α,β-unsaturated carbonyl species. Herein, we report an alternative approach to the preparation of MBH adducts employing an anti-selective direct aldol cascade reaction followed by oxidative elimination. This alternative process is rapid, efficient, and generally applicable, even to β-substituted α,β-unsaturated compounds. </p><p>Progress toward the asymmetric total synthesis of apratoxin D is described. The key step of the synthesis is the asymmetric α,α-bisalkylation of chiral N-amino cyclic carbamate (ACC) hydrazones, a new methodology developed by our group. Herein we demonstrate the utility of this method for convergent total syntheses.</p>","abstract_has_math":false,"creators":["Tarsis, Emily Michelle"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":["Coltart, Don M"],"committee_chairs":[],"committee_members":[],"year":2010,"date_issued":"2010","date_published":"2010","updated_at":"2026-07-24T02:07:10Z","subjects":["Organic Chemistry"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/10161/3074","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Coltart, Don M"]},{"key":"dc:creator","label":"Author","values":["Tarsis, Emily Michelle"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2011-01-06T16:00:37Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2012-12-12T05:30:13Z"]},{"key":"dc:date.issued","label":"Date","values":["2010"]},{"key":"dc:type","label":"Dc Type","values":["Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Organic Chemistry"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/10161/3074"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Cascade reactions, also referred to as domino reactions, have been widely used for the formation of carbon-carbon bonds. This type of reaction has the potential to circumvent protection and deprotection steps, shortening an overall synthetic process.
The Morita-Baylis-Hillman (MBH) reaction is a particularly notable example of an anionic domino reaction which provides straightforward access to β'-hydroxy-α,β-unsaturated carbonyl compounds from aldehydes and α,β-unsaturated carbonyls. However, despite the importance of the Baylis-Hillman reaction, it is slow, reaction yields are quite low, and the process is not general, as it rarely works for β-substituted α,β-unsaturated carbonyl species. Herein, we report an alternative approach to the preparation of MBH adducts employing an anti-selective direct aldol cascade reaction followed by oxidative elimination. This alternative process is rapid, efficient, and generally applicable, even to β-substituted α,β-unsaturated compounds.
Progress toward the asymmetric total synthesis of apratoxin D is described. The key step of the synthesis is the asymmetric α,α-bisalkylation of chiral N-amino cyclic carbamate (ACC) hydrazones, a new methodology developed by our group. Herein we demonstrate the utility of this method for convergent total syntheses.
"]},{"key":"dc:title","label":"Title","values":["New Methods for the α-Functionalization of Thioesters and Activated Hydrazones and an Application Toward the Total Synthesis of Apratoxin D"]}]}],"canonical_facts":{"dc:contributor.advisor":["Coltart, Don M"],"dc:creator":["Tarsis, Emily Michelle"],"dc:date.accessioned":["2011-01-06T16:00:37Z"],"dc:date.available":["2012-12-12T05:30:13Z"],"dc:date.issued":["2010"],"dc:description.abstract":["Cascade reactions, also referred to as domino reactions, have been widely used for the formation of carbon-carbon bonds. This type of reaction has the potential to circumvent protection and deprotection steps, shortening an overall synthetic process.
The Morita-Baylis-Hillman (MBH) reaction is a particularly notable example of an anionic domino reaction which provides straightforward access to β'-hydroxy-α,β-unsaturated carbonyl compounds from aldehydes and α,β-unsaturated carbonyls. However, despite the importance of the Baylis-Hillman reaction, it is slow, reaction yields are quite low, and the process is not general, as it rarely works for β-substituted α,β-unsaturated carbonyl species. Herein, we report an alternative approach to the preparation of MBH adducts employing an anti-selective direct aldol cascade reaction followed by oxidative elimination. This alternative process is rapid, efficient, and generally applicable, even to β-substituted α,β-unsaturated compounds.
Progress toward the asymmetric total synthesis of apratoxin D is described. The key step of the synthesis is the asymmetric α,α-bisalkylation of chiral N-amino cyclic carbamate (ACC) hydrazones, a new methodology developed by our group. Herein we demonstrate the utility of this method for convergent total syntheses.
"],"dc:identifier.uri":["https://hdl.handle.net/10161/3074"],"dc:subject":["Organic Chemistry"],"dc:title":["New Methods for the α-Functionalization of Thioesters and Activated Hydrazones and an Application Toward the Total Synthesis of Apratoxin D"],"dc:type":["Dissertation"]},"updated_at":"2026-07-24T02:07:10Z"}