Lounge area of the old Student Union, Chapman College, Orange, California

Lounge area of the old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Lounge area of the old Student Union, Chapman College, Orange, California

Lounge area of the old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Outside the old student union, Chapman College, Orange, California

Old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Old Student Union patio, Chapman College, Orange, California

Old Student Union patio, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Snack bar inside the old Student Union, Chapman College, Orange, California

Snack bar inside the old Student Union, Chapman College, Orange, California in the 1970s. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Patio area of old Student Union, Chapman College, Orange, California

Patio area of old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Patio area of the old Student Union, Chapman College, Orange, California

Patio area of the old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Hungrey Panther entrance at the old Student Union, Chapman College, Orange, California

Hungrey Panther entrance at the old Student Union, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Old Student Union patio remodel, Chapman College, Orange, California

Old Student Union patio remodel in progress, Chapman College, Orange, California. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Old Student Union patio remodel, Chapman College, Orange, California

Old Student Union patio remodel in progress, Chapman College, Orange, California, 1973. Signage on building also part of the campus renewal. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Old Student Union building and patio remodel, Chapman College, Orange, California

Old Student Union building and patio remodel, Chapman College, Orange, California, 1973. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Renovating the old Student Union patio, Chapman College, Orange, California

Renovating the old Student Union patio, Chapman College, Orange, California, 1973. The Australian tea trees were moved from the music building site. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Renovating the old Student Union patio, Chapman College, Orange, California, 1973

Renovating the old Student Union patio, Chapman College, Orange, California, 1973. The Australian tea trees were moved from the music building site. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Painting signage on old Student Union, Chapman College, Orange, California

Painting signage on old Student Union, Chapman College, Orange, California, as part of a campus renewal project in 1973. Originally the manual arts building and bus repair garage for Orange Union High School. Building annex additions through 1975 increased the size to 19,680 sq. ft. Used as a student union by Chapman College. In 1996 the building became the Cecil B. DeMille Hall, housing the Film and TV department.

Studies toward the total synthesis of natural and unnatural aeruginosins

Nous avons démontré l’utilité du groupement protecteur tert-butylsulfonyle (N-Bus) pour la chimie des acides aminés et des peptides. Celui-ci est préparé en deux étapes, impliquant la réaction d’une amine avec le chlorure de tert-butylsulfinyle, suivie par l’oxydation par du m-CPBA, pour obtenir les tert-butylsulfonamides correspondants avec d’excellents rendements. Le groupement N-Bus peut être clivé par traitement avec 0.1 N TfOH/DCM/anisole à 0oC en 10h pour régénérer le sel d’ammonium. Une variété d’acides aminés N-Bus protégés ainsi que d’autres aminoacides peuvent alors être utilisés pour préparer divers dipeptides et tripeptides. A l’exception du groupe N-Fmoc, les conditions de déprotection du groupe N-Bus clivent également les groupements N-Boc, N-Cbz et O-Bn. Une déprotection sélective et orthogonale des groupes N-Boc, N-Cbz, N-Fmoc et O-Bn est également possible en présence du groupe protecteur N-Bus. Le nouvel acide aminé non-naturel (3R, 2R) 3–méthyl-D-leucine (β-Me-Leu) et son régioisomère 2-méthyle ont été synthétisés par ouverture d’une N-Ts aziridine en présence d’un excès de LiMe2Cu. Chacun des régioisomères du mélange (1:1,2) a été converti en la méthylleucine correspondante, puis couplé à l’acide D-phényllactique puis au motif 2-carboxyperhydroindole 4-amidinobenzamide en présence de DEPBT. Des élaborations ultérieures ont conduit à des analogues peptidiques non-naturels d’aeruginosines telles que la chlorodysinosine A. Les deux analogues ont ensuite été évalués pour leur activité inhibitrice de la thrombine et la trypsine. La présumée aeruginosine 3-sulfate 205B et son anomère β ont été synthétisés avec succès à partir de 5 sous-unités : la 3-chloroleucine, l’acide D-phényllactique, le D-xylose, le 2-carboxy-6-hydroxyoctahydroindole et l’agmatine. La comparaison des données RMN 1H et 13C reportées avec celles obtenues avec l’aeruginosine synthétique 205B révèle une différence majeure pour la position du groupe présumé 3'-sulfate sur l’unité D-xylopyranosyle. Nous avons alors synthétisés les dérivés méthyl-α-D-xylopyranosides avec un groupement sulfate à chacune des positions hydroxyles, afin de démontrer sans ambiguïté la présence du sulfate en position C-4' par comparaison des données spectroscopiques RMN 1H et 13C. La structure de l’aeruginosine 205B a alors été révisée. Une des étapes-clés de cette synthèse consiste en la formation du glycoside avec le groupe hydroxyle en C-6 orienté en axial sur la sous-unité Choi. Le 2-thiopyridylcarbonate s’est avéré une méthode efficace pour l’activation anomérique. Le traitement par AgOTf et la tétraméthylurée en solution dans un mélange éther-DCM permet d’obtenir l’anomère α désiré, qui peut alors être aisément séparé de l’anomère β par chromatographie