Diversity in Catalytic Reactions of Propargylic Diazoesters

Abstract Title of Document: Diversity in Catalytic Reactions of Propargylic Diazoesters Huang Qiu, Doctor of Philosophy, 2016 Directed By: Professor Michael P. Doyle, Department of Chemistry and Biochemistry Propargylic aryldiazoesters, which possess multiple reactive functional groups in a single molecule, were expected to undergo divergent reaction pathways as a function of catalysts. A variety of transition metal complexes including rhodium(II), palladium(II), silver(I), mercury(II), copper(I and II), and cationic gold (I) complexes have been examined to be effective in the catalytic domino reactions of propargylic aryldiazoesters. An unexpected Lewis acid catalyzed pathway was also discovered by using FeCl3 as the catalyst. Under the catalysis of selected gold catalysts, propargylic aryldiazoesters exist in equilibrium with 1-aryl-1,2-dien-1-yl diazoacetate allenes that are rapidly formed at room temperature through 1,3-acyloxy migration. The newly formed allenes further undergo a metal-free rearrangement in which the terminal nitrogen of the diazo functional group adds to the central carbon of the allene initiating a sequence of bond forming reactions resulting in the production of 1,5-dihydro-4H-pyrazol-4-ones in good yields. These 1,5-dihydro-4H-pyrazol-4-ones undergo intramolecular 1,3-acyl migration to form an equilibrium mixture or quantitatively transfer the acyl group to an external nucleophile with formation of 4-hydroxypyrazoles. In the presence of a pyridine-N-oxide, both E- and Z-1,3-dienyl aryldiazoacetates are formed in high combined yields by Au(I)-catalyzed rearrangement of propargyl arylyldiazoacetates at short reaction times. Under thermal reactions the E-isomers form the products from intramolecular [4+2]-cycloaddition with H‡298 = 15.6 kcal/mol and S‡298= -27.3 cal/ (mol•degree). The Z-isomer is inert to [4+2]-cycloaddition under these conditions. The Hammett relationships from aryl-substituted diazo esters ( = +0.89) and aryl-substituted dienes ( = -1.65) are consistent with the dipolar nature of this transformation. An unexpected reaction for the synthesis of seven-membered conjugated 1,4-diketones from propargylic diazoesters with unsaturated imines was disclosed. To undergo this process vinyl gold carbene intermediates generated by 1,2-acyloxy migration of propargylic aryldiazoesters undergo a formal [4+3]-cycloaddition, and the resulting aryldiazoesters tethered dihydroazepines undergo an intricate metal-free process to form observed seven-membered conjugated 1,4-diketones with moderate to high yields.

ENGINEERING HIERARCHICAL MESO-/MICROPOROUS LAMELLAR ZEOLITES WITH VARIABLE TEXTURAL AND CATALYTIC PROPERTIES

Meso-/microporous zeolites combine the charactersitics of well-defined micropores of zeolite with efficient mass transfer consequences of mesopores to increase the efficiency of the catalysts in reactions involving bulky molecules. Different methods such as demetallation and templating have been explored for the synthesis of meso-/microporous zeolites. However, they all have limitations in production of meso-/microporous zeolites with tunable textural and catalytic properties using few synthesis steps. To address this challenge, a simple one-step dual template synthesis approach has been developed in this work to engineer lamellar meso-/microporous zeolites structures with tunable textural and catalytic properties. First, one-step dual template synthesis of meso-/microporous mordenite framework inverted (MFI) zeolite structures was investigated. Tetrapropyl ammonium hydroxide (TPAOH) and diquaternary ammonium surfactant ([C22H45-N+(CH3)2-C6H12-N+(CH3)2-C6H13]Br2, C22-6-6) were used as templates to produce micropores and mesopores, respectively. The variation in concentration ratios of dual templates and hydrothermal synthesis conditions resulted in production of multi-lamellar MFI and the hybrid lamellar-bulk MFI (HLBM) zeolite structures. The relationship between the morphology, porosity, acidity, and catalytic properties of these catalysts was systematically studied. Then, the validity of the proposed synthesis approach for production of other types of zeolites composites was examined by creating a meso-/microporous bulk polymorph A (BEA)-lamellar MFI (BBLM) composite. The resulted composite samples showed higher catalytic stability compared to their single component zeolites. The studies demonstrated the high potential of the one-step dual template synthesis procedure for engineering the textural and catalytic properties of the synthesized zeolites.