Thesis (Ph. D.)--University of Wisconsin--Madison, 1980. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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

Thesis (Ph. D.)--University of Wisconsin--Madison, 1985. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

Thesis (M.S.)--University of Wisconsin--Madison, 1962. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaf 39).

Thesis (M.S.)--University of Wisconsin--Madison, 1961. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 37-39).

Thesis (M.S.)--University of Wisconsin--Madison, 1962. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 38-41).

The syntheses of glycos-3-yl amino acids, 2-deoxy glycos-3-yl amino acids,and deoxy amino uronic acid derivatives (homologous of the sugar moiety of the polyoxins) are reported. 5,3-Spiro-pyrrolidone carbohydrate derivatives, formed by intramolecular cyclization from doubly branched-chain a, y-diami.no acids, are also described. The ketose, 1,2:5,6-di-O-isopropylidene-a-D-ribo-hexofuranos-3-ulose (8)'', was condensed with 2-phenyl-5 (4)-oxazolinone (89), in the presence of lead (II) acetate as catalyst, to yield (E)-and (Z)-2-phenyl-4- (1,2:5,6-di-O-isopropylidene-a-D-ribo-hexofuranos-3-ylidene)-5(4) oxazolone (143) and (144), as a 1:1 mixture,in a 75% yield. The stereo-specific synthesis of 143 was achieved by changing the reaction solvent from dimethoxyethane to tetrahydrofuran. Methanolysis of a mixture of 143 and 144 afforded a mixture of (E)- and (Z)-methyl-N-benzamido-a-(1,2:5,6-di-O-isopropylidene-a-D-ribo-hexofuranos-3-ylidene)glycinate (145) and (146) in a 90% yield. Catalytic hydrogenation of the mixture of 145 and 146 afforded methyl-D-2 (and L-2) -3-deoxy-1,2 :5 ,6-di-0_-isopropylidene-a-D-allofuranos-3-yl)-N-benzoylglycinate (147) and (148) which were separated by silica gel chromatography. Methyl 4,6-0-benzylidene-2-deoxy-q-D-erythro-hexopyranoside-3-ulose (153), was allowed to react with 2-phenyl-5(4)-oxazolone (89) to yield (E)- and (Z)-2-phenyl~4-(methyl-4,6-0-benzylidene-2,3-dideoxy-a-D-erythro-hexopyranos-3-ylidene)-5(4)-oxazolone (154) and (155) in 13% and 27% yields, respectively. Methanolysis of 154 and 155_ afforded (Eland (Z)-methyl-N-benzamido-a-(methyl-4,6-0-benzylidene-2,3-dideoxy-a-D-erythro-hexopyranos-3-ylidene)glycinate (156) and (157) in quantitative yields. Compound 156 was catalytically"hydrogenated to afford methyl-D-2-(methyl-4,6-0-cyclohexylmethylidene-2,3-dideoxy-q-g-arabino-hexopyranos-3-yl)-N-cyclohexylcarboxylglycinate (167) in a 71% yield. Similarly, _15_7 afforded methyl-D-2- (methyl-4 ,6-0-cyclohexylmethylidene-2 , 3-dideoxy-q-D-ribo-hexopyranos- 5-yl) -N-cyclohexylcarboxylglycinate (170) in a 68% yield. 2-Phenyl-5(4)-oxazolone (89) was condensed with 3-0-benzyl-l,2-O-isopropylidene-q-g-xylo-pentodialdo-1,4-furanose (173), prepared by known procedures, to afford a mixture of (E)- and (Z)-4-(3-0_-benzyl-5-deoxy-1,2-0-isopropylidene-q-D-xylofuranos-S- ylidene)-2-phenyl-5(4)-oxazolone (174) and (175) in a 45% yield. Methanolysis of the mixture of 174 and 175 afforded (E)- and (Z)-methyl-6-N-benzamido-3-0-benzyl-5,6-dideoxy-l,2-0-isopropylidene-q-D-xylo-heptofur-5-enuronate (176) and (177) in an 85% yield. Hydrogenation followed by hydrogenolysis of the mixture of 176 and 177 gave a mixture of methyl-6-N-benzamido-5,6-dideoxy - 1,2-0-isopropy'lidene-a-D-gluco (and g-L-ido) -heptofuranuronat (180) and (181) . Transesterification of 180 and 181 afforded the ethyl esters which were separated into pure ethyl-6-N-benzamido-5,6-dideoxy-1,2-0-isopropylidene-a-D-gluco (and g-L-ido)-heptofuranuronate (182) and (183) by fractional crystallization. Compound 183 was hydrolyzed in hot aqueous ethanolic barium hydroxide solution to afford 6-amino-5,6-dideoxy-1,2-0-isopropylidene-g-L-ido-heptofuranuronic acid (184) in a 77% yield. The 1,3-dipolar addition of diazomethane to (Z)-3-deoxy-1,2:5,6-di-0-isopropylidene-3-C-methoxycarbonylmethylene-a-g-ribo-hexofuranose (13) , prepared from 8_ by application of the Wittig reaction, afforded a mixture of spiro-AA- and A^-pyrazolines, which were hydrogenated at high pressure with Raney nickel, to afford spiro-3,4'-S_- (3,3-dideoxy-1,2:5,6-di-O-isopropylidene-q-p-ribo-hexofuranose)-3'-R-amino-2'-pyrrolidone (192) , spiro-3,4'-S~(3,3-dideoxy-l,2:5,6~di-0-isop ropy lidene-a-D-ribo--hexo furanose)-3'-S_-amino-2'pyrrolidone (195) , spiro- 3,4' - R- (3, 3-dideoxy-l ,2 :5 ,6-di-^-isopi'opylidene-a-D-ri_bo_-hexofuranose)-3'-R-amino-2'-pyrrolidone (194) , and spiro-3,4*-R-(3, 3-dideoxy-1,2:5,6-di-0-isopropylidene-a-p-ribo-hexofuranose)- 3'-S-amino-2'-pyrrolidone (195) in yields of 16, 32, 14, and 18%^respectively. Compounds 192, 195, 194, and 195 were acetylated to yield the crystalline derivatives 196, 197.. 198, and 199, Selective de-0-i sop ropy l.i den at ion of compound 196 followed by oxidative cleavage with sodium meta-periodate gave an aminal 200 which was acetylated to afford spiro-3,4' -S_- (3, 3-dideoxy- 1,2-0-isopropylidene-a-D-erythro-pentodia.ldo-1,4-furanose)-3'-R-acetamido-2'-pyrrolidone 3',5 - R-aminal-5,1'-diacetate (202). Compound 19 7 was^selectively de-O-isopropylidenated and oxidized with periodate to yield spiro-3 ,4 '-S-(3,3-dideoxy--1,2-0-isopropylidene-a-D-erythro-pentodialdo-1,4-furanose) -3' -S_- acetamido-2 ' -pyrrolidone (201) . Complete de-0_-isopropylidenation of 197 afforded spiro- 3,4'-S_~ (3,3-dideoxy-g-D-ribo-hexopyranose) -3' -S_-acetamido-2 ' -pyrrolidone (203) in a 30% yield. An optically active amino acid Wittig reagent was prepared as follows. L-Cystine diethyl ester dihydrochloride (205) was chlorinated to yield 3-chloro-L-alanine ethyl ester hydrochloride (206) which was converted to N-acetyl-g-chloro-L-alanine ethyl ester (207). Compound 207 was reacted with tr:i phenyl nhosplunc and sodium iodide to afford cthyl-N-acetyl-3- (triphenyJphosphoniuiniodo)-a-L-a] an ate (204) in a 51% yield. / Science, Faculty of / Chemistry, Department of / Graduate

Modern concepts of the structure, function and metabolism of proteins have evolved painstakingly through the centuries. In September, 1772, Rutherford discovered the gas which was later named nitrogen by Chaptal in 1790 . The fundamental importance of nitrogen in the body was only appreciated after Gay-Lussac and Thenard had pioneered chemical procedures for organic analysis. Magendie applied this knowledge to dietary constituents and concluded that nitrogen was an essential component of the diet. His early insight into metabolism was depicted in his view that body constituents are continuously being replaced, the rate being dependent on the tissue. In 1838 the term"protein" was coined by Gerard Mulder for substances containing a basic nitrogenous component.

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