dc.contributor.advisor | Mohammad Movassaghi. | en_US |
dc.contributor.author | Schmidt, Michael Anthony, 1980- | en_US |
dc.contributor.other | Massachusetts Institute of Technology. Dept. of Chemistry. | en_US |
dc.date.accessioned | 2008-12-11T18:25:24Z | |
dc.date.available | 2008-12-11T18:25:24Z | |
dc.date.copyright | 2008 | en_US |
dc.date.issued | 2008 | en_US |
dc.identifier.uri | http://hdl.handle.net/1721.1/43773 | |
dc.description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2008. | en_US |
dc.description | Vita. | en_US |
dc.description | Includes bibliographical references. | en_US |
dc.description.abstract | I. The Development of a General Strategy Towards Dimeric Hexahydropyrroloindole Alkaloids. A Concise Total Synthesis of (+)-Chimonanthine, (+)-Folicanthine and (-)Calycanthine. An efficient and convergent strategy for the synthesis of dimeric hexahydropyrroloindole alkaloids is described. The simultaneous formation of the vicinal quaternary stereocenters using a reductive dimerization reaction provides gram-scale access to an optically active key intermediate employed in the synthesis of (+)-chimonanthine, (+)-folicanthine, and (-)calycanthine. II. The Development of a General Strategy Towards Dimeric Hexahydropyrroloindole Alkaloids. A Concise Total Synthesis of (+)-WIN 64821, (-)-Ditryptophenaline and (-)-1'(2-Phenylethylene)-ditryptophenaline. The concise enantioselective total synthesis of (+)-WIN 64821 and (-)-ditryptophenaline in six and seven steps, respectively, from commercially available amino acid derivatives is described. The gram-scale synthesis of key intermediates and simultaneous introduction of the vicinal quaternary stereocenters provides a highly effective and preparative synthesis of these natural alkaloids. Additionally, the synthesis and structural confirmation of the natural alkaloid (-)-1 '-(2-phenylethylene)-ditryptophenaline is described. III. N-Heterocyclic Carbene-Alcohol Hydrogen Bonds. Studies and Application in the Amidation of Unactivated Esters. A single-step and catalytic amidation of unactivated esters with amino alcohols is described. Treatment of equimolar quantities of amino alcohols and unactivated esters with N,Nbismestiylimidazolylidene (5 mol%) affords the desired amides in high yield under mild reaction conditions. | en_US |
dc.description.abstract | (cont.) The compatibility of the present methodology with a wide range of functional groups, heterocycles, and optically active substrates in addition to both aromatic and aliphatic esters is noteworthy. Preliminary data regarding an unprecedented hydrogen-bonded carbene-alcohol complex is reported. Further investigation of this hydrogen bond revealed steric and electronic influences on the nature of this bond, cumulating in discovery of a practical metal free method for the stabilization and storage of these nitrogen heterocyclic carbenes. Also described is a method for the synthesis of optically active imidazo-[1,5-a]-pyridinium salts as precursors to optically active nitrogen heterocyclic carbenes. | en_US |
dc.description.statementofresponsibility | by Michael Anthony Schmidt. | en_US |
dc.format.extent | 338 p. | en_US |
dc.language.iso | eng | en_US |
dc.publisher | Massachusetts Institute of Technology | en_US |
dc.rights | M.I.T. theses are protected by
copyright. They may be viewed from this source for any purpose, but
reproduction or distribution in any format is prohibited without written
permission. See provided URL for inquiries about permission. | en_US |
dc.rights.uri | http://dspace.mit.edu/handle/1721.1/7582 | en_US |
dc.subject | Chemistry. | en_US |
dc.title | The development of new synthetic strategies and methodologies for complex alkaloid total synthesis : a concise synthesis of (+)-chimonanthine, (+)-WIN 64821, (-)-ditryptophenaline and related alkaloids | en_US |
dc.title.alternative | Concise synthesis of (+)-chimonanthine, (+)-WIN 64821, (-)-ditryptophenaline and related alkaloids | en_US |
dc.type | Thesis | en_US |
dc.description.degree | Ph.D. | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | |
dc.identifier.oclc | 260457144 | en_US |