Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1997. / Includes bibliographical references. / by Joanna R. Long. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2010. / Vita. Cataloged from PDF version of thesis. / Includes bibliographical references. / Chapter I. In the presence of the N-heterocyclic carbene ligand IPr, the nickel(0)-catalyzed coupling reaction of a-olefins and branched aliphatic isocyanates provides c,-unsaturated amides arising from preferential C-C bond formation at the 2-position of the olefin. This sense of regioselectivity contrasts with the observed carboxamidation at the 1-position of the olefin when phosphine ligands are used. In this reaction, a simple alkene acts as the functional equivalent of a 2-alkenylmetal reagent. ... Chapter II. Synthetic studies on the antibiotic natural product ripostatin A have been carried out with the aim of constructing the C9-C1O bond via a nickel(0)-catalyzed coupling reaction of enynes and epoxides developed in our laboratory, followed by rearrangement of the resulting dienylcyclopropane intermediate to afford the skipped 1,4,7-triene. ... A cyclopropyl enyne fragment corresponding to C1-C9 of ripostatin A can be synthesized in high yield over 10 steps and was demonstrated to be a competent substrate for the nickel(0)-catalyzed coupling reaction with a model epoxide. The origin of regioselectivity in this particular transformation is also discussed. ... Several synthetic approaches towards the desired C1O-C26 epoxide fragment have been pursued. The presence of the C19-C20 trisubstituted olefin renders introduction of the epoxide via oxidation of or iodocyclization onto a terminal alkene unsuitable. Access of the epoxide by way of nucleophlic displacement should circumvent these problems. The C13 stereocenter can be set via the allylation and reductive decyanation of a cyanohydrin acetonide. ... A mild, fluoride-promoted decarboxylation enables the construction of the C15-C16 bond via an aldol reaction. This product of this transformation is of the correct oxidation state and three steps removed from the targeted epoxide fragment. / by Kristin D. Schleicher. / Ph.D.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1984. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Includes bibliographical references. / by Dan Imre. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005. / MIT Science Library copy: Issued in leaves, in a 2 v. set. / Also issued in leaves, in a 2 v. set. Vita. / Includes bibliographical references . / I. The Development of Methods for the Iterative Synthesis of Polytetrahydropyrans An iterative method comprising chain homologation, epoxidation, 6-endo cyclization, and protiodesilylation was developed. Notable achievements include the development of a novel propargyl organocopper coupling method, and the complete control of stereoselectivity and regioselectivity during the iterative synthesis of a tristetrahydropyran. The synthesis of the tristetrahydropyran was achieved in 18 total operations. ... (1) homologation (2) epoxidation (3) cyclization (4) protiodesilylation ... II. The Development of a Cascade Synthesis of Polytetrahydropyrans with No Directing Groups at Ring Junctions Cascade approaches to trans-fused tetrahydropyrans were studied. After exploring acid-promoted cascade cyclizations of polyepoxysilanes and polyepoxides without directing groups, the base-promoted cascade cyclization of polyepoxysilanes was realized. In this method, as many as five operations take place in a single step to provide a tristetrahydropyran with no directing groups at any ring junctions. The synthesis of the tristetrahydropyran was accomplished in 11 steps. ... / by Timothy Paul Heffron. / Ph.D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1958. / Vita. / Includes bibliographical references (leaves 103-104). / by Richard Warren Fessenden. / Ph.D.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1934. / Includes bibliographical references (leaf 29). / by Carolyn H. Klein. / M.S.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1995. / Includes bibliographical references. / by David J. Norris. / Ph.D.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005. / Vita. / Includes bibliographical references. / Model studies on the total synthesis of salvilenone, a phenalenone diterpene found in the roots of Salvia miltiorrhiza Bunge, are reported via a double annulation strategy. The key steps in the proposed synthesis involve a regiocontrolled benzannulation involving the photochemical Wolff rearrangement of an a-diazo ketone and an alkoxy acetylene moiety which assembles an aromatic ring in one step from acyclic precursors followed by an intramolecular [4 + 2] cycloaddition of a conjugated enyne and benzyne intermediate. / by HuiWon Choi. / S.M.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2005. / Includes bibliographical references. / The asymmetric biaryl backbone of a dialkylbiphenyl phosphine ligand was developed, synthesized, and resolved. The application of the chiral phosphine ligand to the asymmetric Suzuki-Miyaura cross-coupling reaction was also investigated. This phosphine ligand has yielded promising results in the asymmetric Suzuki-coupling of hindered boronic acids with the electron-rich aryl bromide, 1-bromo-2- methoxynaphthalene, to synthesize biaryls in modest enantioselectivity. / by Satoko Hirai. / S.M.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1998. / Includes bibliographical references. / by Jonas Christopher Peters. / Ph.D.