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A general method for the formation of acetals using chlorotrimethylsilane has been developed. Dioxolanes are formed from most carbonyl groups whereas methyl acetals are only formed from electron-poor carbonyl groups. The intermediacy of a silicon-bound carbonyl species is discussed. / The method has been extended to the formation of esters. In a solution of the alcohol to be esterified, methyl, ethyl, benzyl and 2-trimethylsilylethyl esters are readily formed in the presence of chlorotrimethylsilane. Using ('29)Si-N.M.R., a trimethylsilyl ester has been shown to be an intermediate in the reaction. / The Lewis acid catalyzed condensation of 1,3-bis-trimethylsiloxy-1-methoxy-1,3-butadiene with a variety of dielectrophiles, in a 1,2 relationship, has been investigated. The relative order of electrophilic reactivity towards this compound has been found to be; RR'C(Cl)SC(,6)H(,5) > ArCOCHO > ArCOCHO > RC(OCH(,3))(,2),RC(OCH(,3))SC(,6)H(,5) > RCHCl(,2). The dialkylation of 1,3-bis-trimethylsiloxy-1-methoxy-1,3-butadiene has been shown to lead to hydroxycyclopentenones with the same substitution pattern as the prostaglandins skeleton. Using ('29)Si-N.M.R., the mechanism of this reaction has been shown to proceed in two sequential steps; reaction of the (gamma)-position takes place first to give a titanium-bound intermediate, the thus formed intermediate then undergoes (alpha)-alkylation to give the cyclopentenone compound.

Methyl 4-trimethylsilyl-3-dialkylaminocrotonate is synthesized by the silylation of methyl 3-dialkylaminocrotonate. It reacts with carbonyl electrophiles at its (gamma)-position. The unusual regiochemistry of this reaction is studied and rationalized. It reacts with enamines derived from acyclic ketones or cycloketones of large ring size (of 12 and 15 membered rings) to give aromatic compounds in a 3C + 3C combination and with enamines derived from cycloketones of 5-8 membered rings to give aromatic compounds in a 4C + 2C combination. The mechanism of this cycloaromatization reaction is investigated. / meta-Cyclophanes with a morpholino substituent are synthesized by the above cycloaromatization reaction. These meta-cyclophanes possess planar chirality and are successfully resolved. / A number of metacyclophanes with alkyl substituents at the intraannular position are synthesized. Depending on the ring size and the steric size of the alkyl group, some of them are also resolved. The rotation process of meta-cyclophane is studied through their temperature dependent ('1)H NMR.

Graduation date: 1961

Photocopy of typescript. / Thesis (Ph. D.)--University of Hawaii at Manoa, 1979. / Bibliography: leaves 172-197. / Microfiche. / xii, 179 leaves ill. 29 cm

Typescript. / Thesis (Ph. D.)--University of Hawaii, 1966. / Bibliography: leaves [60]-64. / x, 64 l illus

Typescript. / Thesis (Ph. D.)--University of Hawaii, 1966. / Bibliography: leaves [114]-116. / ix, 116 l illus., tables

Typescript. / Thesis (Ph. D.)--University of Hawaii, 1968. / Bibliography: leaves 100-102. / viii, 102 l graphs, tables