Stereoselective synthesis of substituted hexahydro-3a,4a-diazacyclopentaphenanthren-4-ones and aminoferrocenes

This thesis explored the development of several methodologies for the stereoselective construction of ligand frameworks and some of their applications. The first segment concerns the application of an enantioselective lithiation at an Sp3_ hybridized position adjacent to nitrogen by means of the widely used and typically highly effective enantioselective lithiation with ( -)-sparteine. This investigation was intended to develop a method to install chirality into a system that would be converted into a family of diaminoylidenes for use as phosphine mimics in transition metal catalysis or as nucleophilic reagents. Molecular modeling of the system revealed some key interactions between the substrate and (-)-sparteine that provided general insight into the diamine's mode of action and should lend some predictive value to its future applications. The second portion focuses on the development of methods to access 1,2- disubstituted aminoferrocenes, an underexplored class of metallocenes possessing planar chirality. Two routes were examined involving a diastereoselective and an enantioselective pathway, where the latter method made use of the first BF3-mediated lithiation-substitution to install planar chirality. Key derivatives such as 1,2- aminophosphines, made readily accessible by the new route, were evaluated as ligands for Pd(II), Pt(II) and Ir(I). These complexes show activity in a number of transformations with both achiral and prochiral substrates. Optimization experiments were conducted to prepare enantiomerically enriched 2-substituted-I-aminoferrocenes by direct asymmetric lithiation of BF3-coordinated tertiary aminoferrocenes. A predictive computational model describing the transition state of this reaction was developed in collaboration with Professor Travis Dudding's group (Department of Chemistry, Brock University). The predicted stereochemistry of the process was confirmed by single-crystal X-ray analysis of a 2-phosphino-l-dimethylaminoferrocene derivative. Enantiomerically pure samples of the aminophosphine ligands derived from this new process have given promising preliminary results in the enantioselective hydrogenation of prochiral alkenes and warrant further stUdy in metal-mediated catalysis.

Socially Constructed Environmental Issues and Sport: A Content Analysis of Ski Resort Environmental Communications

Due to the impact of sport on the natural environment (UN, 2010), it is important to examine the interplay between environmental issues and sport (Hums, 2010, Mallen & Chard, 2011; Nauright & Pope, 2009; Ziegler, 2007). This research content analyzed 82 ski resort environmental communications (SRECs). These communications were rated for their prominence, breadth, and depth using the delineation of environmental issues provided by the Sustainable Slopes Program (SSP) Charter. This data was compared to the resorts’ degree of environmentally responsible action as rated by the Ski Area Citizens’ Coalition (SACC). An adaptation of Hudson and Miller's (2005) model was then used to classify the ski resorts as inactive, reactive, exploitive, or proactive in their environmental activities. Recommendations have been made for standardization and transparency in environmental disclosures and an environmental management system to aid ski resorts in moving from ad hoc processes to a systematic and comprehensive framework for improving environmental performance.

Hydrosilylation and hydroboration catalyzed by imido-hydride complexes of molybdenum (IV)

This thesis describes the synthesis, structural studies, stoichiometric and catalytic reactivity of novel Mo(IV) imido hydride complexes (Cp)(ArN)Mo(H)(PMe3) (1) and (Tp )(ArN)Mo(H)(PMe3) (2). Both 1 and 2 catalyze hydrosilylation of a variety of carbonyls. Detailed kinetic and DFT studies found that 1 reacts by an unexpected associative mechanism, which does not involve Si-H addition either to the imido group or the metal. Despite 1 being a d2 complex, its reaction with PhSiH3 proceeds via a a-bond metathesis mechanism giving the silyl derivative (Cp )(ArN)Mo(SiH2Ph)(PMe3). In the presence of BPh3 reaction of 1 with PhSiH3 results in formation of (Cp)(ArN)Mo(SiH2Ph)(H)2 and (Cp)(ArN)Mo(SiH2Ph)2(H), the first examples ofMo(VI) silyl hydrides. AI: 1 : 1 reaction between 2, PhSiD3 and carbonyl substrate established that hydrosilylation is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional mechanism based on carbonyl insertion carbonyl. As 2 is nomeactive to both the silane and ketone, the only mechanistic alternative we are left with is that the metal center activates the carbonyl as a Lewis acid. The analogous nonhydride mechanism was observed for the catalysis by (ArN)Mo(H)(CI)(PMe3), (Ph3P)2(I)(O)Re(H)(OSiMe2Ph) and (PPh3CuH)6. Complex 2 also catalyzes hydroboration of carbonyls and nitriles. We report the first case of metal-catalyzed hydroboration of nitriles as well as hydroboration of carbonyls at very mild conditions. Conversion of carbonyl functions can be performed with high selectivities in the presence of nitrile groups. This thesis also reports the first case of the HlH exchange between H2 and Si-H of silanes mediated by Lewis acids such as Mo(IV) , Re(V) , Cu(I) , Zn(II) complexes, B(C6Fs)3 and BPh3.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Synthesis of a 7-Membered Biaryl Guanidine Catalyst and its Use in the Vinylogous Aldol Reaction

The present thesis outlines the preparation of a 7-membered guanidine. Initial efforts to obtain this guanidine via 2-chloro-1,3-dimethylimidazolinium chloride induced ring forming chemistry failed to provide the target in a reproducible fashion. Changing strategies, we were able to obtain the desired guanidine through CuCl mediated amination of a 7-membered thiourea intermediate to arrive at the target. In addition, the catalytic activity of this compound was evaluated in a vinylogous aldol reaction of dibromofuranone and four aromatic aldehydes to generate chiral γ-butenolides with modest to good enantiomeric excess. It was found that electron-poor aldehydes resulted in higher, 81% ee, whereas electron rich aldehydes led to low, 41% ee, levels of enantiomeric excess.

Cyclotetrasiloxane Frameworks for the Chemoenzymatic Synthesis of Oligoesters

Immobilized lipase B from Candida antarctica (Novozym® 435, N435) was utilized as part of a chemoenzymatic strategy for the synthesis of branched polyesters based on a cyclotetrasiloxane core in the absence of solvent. Nuclear magnetic resonance spectroscopy and matrix-assisted laser desorption ionization time-of-flight mass spectrometry were utilized to monitor the reactions between tetraester cyclotetrasiloxanes and aliphatic diols. The enzyme-mediated esterification reactions can achieve 65– 80% consumption of starting materials in 24–48 h. Longer reaction times, 72–96 h, resulted in the formation of cross-linked gel-like networks. Gel permeation chromatography of the polymers indicated that the masses were Mw ¼ 11 400, 13 100, and 19 400 g mol 1 for the substrate pairs of C7D4 ester/ octane-1,8-diol, C10D4 ester/pentane-1,5-diol and C10D4 ester/octane-1,8-diol respectively, after 48 h. Extending the polymerization for an additional 24 h with the C10D4 ester/octane-1,8-diol pair gave Mw ¼ 86 800 g mol 1. To the best of our knowledge this represents the first report using lipase catalysis to produce branched polymers that are built from a cyclotetrasiloxane core.

A Bicyclic L-Proline Derived Chiral Auxiliary for Asymmetric Synthesis

This thesis describes the use of an L−proline-derived chiral auxiliary for diastereoselective lithiation and ligand synthesis. Such compounds have been utilized in the Metallinos research group previously for the synthesis of N−substituted planar chiral ferrocenes. The first project describes the use of this chiral auxiliary as a directing group for N−benzyl substitution, providing products in up to 10:1 diastereomeric ratio (dr). These derivatives may serve as chiral ylidene precursors to serve as ligands in transition metal catalysis. In addition, an N−substituted planar chiral ferrocene ylidene ligand derived from the same chiral auxiliary was used to prepare rhodium complexes that were explored as potential catalysts for asymmetric hydroformylation.