Thesis (Honors)--College of William and Mary, 2008. / Includes bibliographical references (leaves 78-79). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1966. / Vita. Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--Catholic University of America, 1942. / Reproduced from type-written copy. "Literature cited": p. 41-43.

A new synthetic route to cyclophanenes 56, starting from an appropriate 2,6-dihalogen-substituted toluene via monothiacyclophanes as intermediate compounds, was developed. By this method, anti-5,8,13-16-tetramethyl [2,2] (1,3)cyclophan-1-ene, 56b, and anti-4,6,8,12,14,16-hexa-methyl [2,2] (1,3)cyclophan-1-ene, 56c, were first synthesized as well as three new monothiacyclophanes, anti-9,17-dimethyl-2-thia [3,2] (1,3) cyclophane, 72a, anti-6,9,14,17-tetramethyl-2-thia [3,2] (1,3) cyclophane, 72b, anti-5,7,9,13,15,17-hexamethyl-2-thia [3,2] (1,3) cyclophane, 72c. An X-ray structural determination of the monothiacyclophane 72a revealed an anti-stepped geometry of the molecule and that the aromatic rings were bent outward in a slightly distorted boat form. A reciprocal relationship between deviations of the inner carbons from their basal planes and distances between the inner carbons was found by comparison of X-ray data of four metacyclophanes. Several tricarbonylchromium(0) and η5-cyclopentadienyl-iron(I) complexes of cyclophanenes 56 were also prepared for the first time. The complexation effect and ring current reduction effects in these complexes were investigated through studies of their proton nmr spectra. An X-ray structure analysis of anti-8,16-dimethyl [2,2] (1,3) cyclophan-1-ene-cyclopentadienyliron(I), 105a, was determined and it was found that the bridge double bond (1.345A) has a cis geometry but with very large torsional angles: 24.7° for C-C=C-C and 41.6° for H-C=C-H. The bridge chemistry of cyclophanenes 56 and their metal complexes was investigated through some selected reactions. It was found that the cyclophanenes 56 were easily oxidized in attempted electrophilic additions to the bridge double bond. Bromination of the cyclophanene-iron complexes 105b and 105c did give the desired bromine adducts. However, it was found that the reactivity of the bridge double bond in cyclophanenes 56 is very low since most of the attempted reactions failed to give the desired products. The first synthesis of the (η6, η6-anti-4,6,8-trimethyl [2,2] (1,3) cyclophan-1,9-diene)-bis(tricarbonylchromium(0)), 133, was achieved through the dithiacyclophane route. An X-ray structure analysis of 133 was also determined and found that the two aromatic rings were inclined at 19.8° with respect to each other. / Graduate

This thesis describes the preparation of 5-chloro-2-trimethyl-stannyl-1-pentene (111) and its conversion into 5-chloro-2-lithio-1-pentene (112). The latter reagent, which reacts smoothly with cyclohex-anone at -78°C to give 5-chloro-2-(1-hydroxycyclohexyl)-1-pentene (132), was found to be thermally unstable at temperatures higher than -63°C. Reagent (112) was transformed into the Grignard reagent (144) and the organocopper-phosphine complex reagent (145). Conjugate addition of reagents (144) and/or (145) to cyclic enones under appropriate conditions followed by cyclization of the resultant products, effected useful methylenecyclohexane annulation sequences [(104) → (116)]. This methylenecyclohexane annulation method served as one of the two key steps in the syntheses of (±)-axamide-1 (174), (±)-axiso-nitrile-1 (173), and the corresponding C-10 epimers. Thus, copper(I)-catalyzed addition of the Grignard reagent (144) to 2-methyl-2-cyclo-penten-1-one (152), followed by cyclization of the resultant chloro ketone (159), gave the annulation product (170), which was converted into the enone (203). The other key step in the projected synthesis, which involved TiC1₄-catalyzed conjugate addition of the bis(trimethyl-silyl) ketene acetal (226) to the enone (203), provided a mixture of the keto acids (222) and (223). With appropriate functional group manipulations, (222) was converted into (±)-axamide-1 (174) and (±)-axisonitrile (173), while (223) was converted into (±)-10-epi-axamide-1 (224) and (±)-10-epi-axisonitrile-1 (225). [Formula Omitted] / Science, Faculty of / Chemistry, Department of / Graduate

No description available.

No description available.

Call number: LD2668 .T4 1955 G35 / Master of Science

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

 A palladium-catalyzed oxidative cascade cyclization reaction has been developed to prepare pyrrolizidine and indolizidine derivatives from simple aliphatic alkenyl amides 2.1ak in one step in moderate to good yields, using Pd(TFA)2 as the catalyst and molecular oxygen (1 atm) as a green oxidant. This cascade cyclization can also proceed for ring-containing unsaturated amides 2.1ln to afford azatricyclic systems. Palladium(II)-catalyzed dehydrohalogenation cascade cyclization reactions have been developed to synthesize polycyclic pyrrolizidine derivatives from iodoalkenylanilides 4.1ai in satisfactory to excellent yields under mild conditions. This reaction produces two stereocenters in one step and only one single diastereomer was obtained in the cyclization of 4.1. The reaction is proposed to proceed through an organopalladium(IV) species, formed by oxidative addition after the aminopalladation. This organopalladium(IV) species then undergoes reductive elimination to give the cyclized product. This cyclization is a fast and efficient way to construct natural alkaloids that contain pyrrolizidine or indolizidine cores. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy