Phospha-adamantanes as ligands for palladium-catalyzed cross-coupling reactions

New and robust methodologies have been designed for palladium-catalyzed crosscoupling reactions involving·a novel·class oftertiary phosphine ligand incorporating a phospha-adamantane framework. It has been realized that bulky, electron-rich phosphines, when used as ligands for palladium, allow for cross-coupling reactions involving even the less reactive aryl halide substrates with a variety of coupling partners. In an effort to design new ligands suitable for carrying out cross-coupling transformations, the secondary phosphine, 1,3,5,7-tetramethyl-2,4,8-trioxa-6phosphaadamantane was converted into a number of tertiary phosphine derivatives. The ability of these tertiary phosphaadamantanes to act as effective ligands in the palladiumcatalyzed Suzuki cross-coupling was examined. 1,3,5,7-Tetramethyl-6-phenyl-2,4,8trioxa- 6-phosphaadamantane (PA-Ph) used in combination with Pdz(dba)3permitted the reaction of an array of aryl iodides, bromides and chlorides with a variety arylboronic acids to give biaryls in good to excellent yields. Subsequently, palladium complexes of PA-Ph were prepared and isolated in high yields as air stable palladium bisphosphine complexes. Two different kinds of crystals were isolated and upon characterization revealed two complexes, Pd(PA-Ph)z.dba and Pd(PA-Ph)zOz. Preliminary screening for their catalytic activity indicated that the former is more reactive than the latter. Pd(PAPh) z.dba was applied as the catalyst for Sonogashira cross-coupling reactions of aryl iodides and bromides and in the reactions of aryl bromides and chlorides with ketones to give a-arylated ketones at mild temperatures in high yields.

Phospha-adamantane ligands and phosphorous ionic liquids for palladium-catalyzed cross-coupling reactions /

New and robust methodologies have been designed for palladiumcatalyzed cross-coupling reactions involving a library of novel tertiary phosphine ligands incorporating a phospha-adamantane framework. The secondary phosphine, l,3,5,7-tetramethyl-2,4,8-trioxa-6-phospha-adamantane was converted into a small library of tertiary phosphine derivatives and the ability of these tertiary phosphaadamantanes to act as effective ligands in the palladium-catalyzed amination reaction and p-alkyl-Suzuki cross-coupling was examined. l,3,5,7-Tetramethyl-6- phenyl-2,4,8-trioxa-6-phosphaadamantane (PA-Ph) used in combination with Pd2(dba)3 CHCI3 facilitated the reaction of an array of aryl iodides, bromides and chlorides with a variety secondary and primary amines to give tertiary and secondary amines respectively in good to excellent yields. 8-(2,4-Dimethoxyphenyl)- l,3,5,7-tetramethyl-2,4,6-trioxa-8-phospha-tricyclo[3.3.1.1*3,7*]decane used in combination with Pd(0Ac)2 permitted the reaction of an array of alkyl iodides, and bromides with a variety aryl boronic acids and alkyl 9-BBN compounds in good to excellent yields. Subsequent to this work, the use of phosphorous based ionic liquids, specifically tetradecyltrihexylphosphonium chloride (THPC), in the Heck reaction provided good to excellent yields in the coupling of aryl iodides and bromides with a variety of olefins.

Personal soundtracks on public transit : personal listening devices and socio-spatial negotiations of students' bus journeys

One way of exploring the power of sound in the experience and constitution of space is through the phenomenon of personal listening devices (PLDs) in public environments. In this thesis, I draw from in-depth interviews with eleven Brock University students in S1. Catharines, Ontario, to show how PLDs (such as MP3 players like the iPod) are used to create personalized soundscapes and mediate their public transit journeys. I discuss how my interview participants experience the space-time of public transit, and show how PLDs are used to mediate these experiences in acoustic and non-acoustic ways. PLD use demonstrates that acoustic and environmental experiences are co-constitutive, which highlights a kinaesthetic quality of the transit-space. My empirical findings show that PLDs transform space, particularly by overlapping public and private appropriations of the bus. I use these empirical findings to discuss the PLD phenomenon in the theoretical context of spatiality, and more specifically, acoustic space. J develop the ontological notion of acoustic space, stating that space shares many of the properties of sound, and argue that sound is a rich epistemological tool for understanding and explaining our everyday experiences.

Sloppy Joe's Bar, Season 1933

A drink manual for the establishment Sloppy Joe's Bar in Havana, Cuba. The manual is pocket size and contains 40 pages of drink recipes. The first few pages describe the bar in Havana, Cuba along with a brief biography of Jose Abeal (Sloppy Joe).

Metal Bar - P. C. Band, Toronto, Ontario

Metal bar, 2 cm x 6 1/2 cm, with the words "P.C. Band, Toronto, Ontario" engraved on it.

Diploma (vellum) from the Bar of Lower Canada to Edward Bradley Parkin of Quebec

Diploma (vellum) from the Bar of Lower Canada to Edward Bradley Parkin of Quebec conferring upon him the right of practicing as an Advocate, Barrister, Attorney, Solicitor and Proctor-at-Law in all courts in Lower Canada, June 4, 1866.