The application of the structural correlation method to determine the reaction coordinate for a putative ring closure reaction

The cr ystal structure of the compound 2-benzoylethylidene-3-(2,4- dibromophenyl)-2,3-dihydro-5-phenyl-l,3,4-thiadiazole* C23H16Br2NZOS (BRMEO) has been determined by using three dimensiona l x-ray diffraction data. The crys tal form is monoclinic, space group P21/c, a = 17.492(4), o -.t' 0 R 0 b =: 16.979(1), c = 14.962(1) A, "X. =o= 90 ',= 106.46(1) , z = 8, graphite-monochromatized Mo~ rad iation, Jl= 0.710J3~, D = 1.62g/cc and o D = 1.65g/cc. The data were col lected on ~ Nonius CAD-4 c diffractometer. The following atoms were made anisotropic: Br, S, N, 0, C7, and C14-C16 for each i ndependent molecu le ; the rest were left isotropic. For 3112 independent refl ec tions with F > 6G\F), R == 0.057. The compound has two independent molecules within the asymmetric unit. Two different conformers were observed which pack well together. /l The S---O interaction distances of 2.493(6) and 2 . 478(7) A were observed for molecules A and B respectively. These values are consistent with earlier findings for 2-benzoylmethylene-3-(2,4-dibromophenyl)- ~~ 2,3-dihydro-5-phenyl-l,3,4-thiadiazole C22H14Br2N20S (BRPHO) and 2-benzoylpropylidene-3-(2,4-dibromophenyl)-2,3-dihydroiii ,'r 5-phenyl-l,3,4-thiadiazole C24H18Br2N20S (BRPETO ) where S---O distances are l ess than the van der Waals (3.251\) but greater than those expected for () a single bond (1.50A). From the results and the literature it appears obvious that the energy/reaction coordinate pathway has a minimum between the end structures (the mono- and bicyclic compounds). * See reference (21) for nomenclature.

Chemoenzymatic Total Synthesis of Morphine alkaloids: Synthesis of Dihydrocodeine and Hydrocodone via a Double Claisen Strategy and ent-Hydromorphone via an Oxidative Dearomatization/intramolecular [4+2] Cycloaddition

This thesis describes the chemoenzymatic synthesis of three morphine alkaloids. The total synthesis of dihydrocodeine and hydrocodone was accomplished starting from bromobenzene in 16 and 17 steps, respectively. The key steps included a microbial oxidation of bromobenzene by E. coli JM109 (pDTG601A), a Kazmaier-Claisen rearrangement of glycinate ester to generate C-9 and C-14 stereo centers, a Johnson-Claisen rearrangement to set the C-13 quaternary center, and a C-10/C-11 ring closure via a Friedel-Crafts reaction. In addition, the total synthesis of ent-hydromorphone starting from β-bromoethylbenzene in 12 steps is also described. The key reactions included the enzymatic dihydroxylation of β-bromoethylbenzene to the corresponding cis-cyclohexadienediol, a Mitsunobu reaction, and an oxidative dearomatization followed by an intramolecular [4+2] cycloaddition.

Letter - E.C. Schmon to Arthur A. Schmon, 14 February 1918

The letter discusses Valentine's Day and she has drawn hearts in red ink. She also describes the events of the previous day: Red Cross work, lunch at YWCA, Club meeting. The letter also includes a list of items in a package she has sent to Arthur. The letter is labelled number 56.

Letter - E.C. Schmon to Arthur A. Schmon, 14 June 1918

Eleanore Celeste has been to visit Arthur Schmon's parents. His father has not been feeling well and takes a week vacation per month. His mother worries because the checks Arthur sends do not come when they should. Eleanore Celeste requests that Arthur write to Washington to have it straightened out. She also mentions her family and who they are visiting over the next week. This letter is labelled number 114.

Letter - E.C. Schmon to Arthur A. Schmon, 14 February 1920

This letter is decorated for Valentine's Day. There is a red cut out hard included that reads "To my Valentine from your Valentine xxxxxx". The second part of the letter talks about how to get to Shelter Bay and Eleanore Celeste remarks "So you do not think it advisable for me to make the trip to Shelter Bay by dog team! Let me tell you dearest, that I wouldn't mind if I had to walk there." These letters are labelled number 126 and 127.

Letter - E.C. Schmon to Arthur A. Schmon, 14 & 15 May 1919

Eleanore Celeste mentions that Arthur is to return in July. She discusses the way the troops are returning to New York and New Jersey and the discharge process. These letters are labelled number 279 and 280.

Letter - E.C. Schmon to Arthur A. Schmon, 14 March 1917

The letter is a thank you for a book Arthur has sent to Eleanore Celeste. The title of the book is not mentioned.