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.

Exploring the use of effective learning strategies to increase students' reading comprehension and test taking skills /

This study examined the effects of providing students with explicit instruction in how to use a repertoire of reading comprehension strategies and test taking skills when reading and responding to three types of questions (direct, inferential, critical). Specifically, the study examined whether providing students with a "model" of how to read and respond to the text and to the comprehension questions improved their reading comprehension relative to providing them with implicit instruction on reading comprehension strategies and test taking skills. Students' reading comprehension and test taking performance scores were compared as a function of instructional condition. Students from 2 grade 8 classes participated in this study. The reading component of the Canadian Achievement Tests, Third Edition (CAT/3) was used to identify students' level of reading comprehension prior to the formal instructional sessions. Students received either explicit instruction, which involved modelling, or implicit instruction, which consisted of review and discussion of the strategies to be used. Comprehension was measured through the administration of formative tests after each instructional session. The formative tests consisted of reading comprehension questions pertaining to a specific form of text (narrative, informational, graphic). In addition, students completed 3 summative tests and a delayed comprehension test which consisted of the alternative version of the CAT/3 standardized reading assessment. These data served as a posttest measure to determine whether students had shown an improvement in their reading comprehension skills as a result of the program delivery. There were significant differences in students' Canadian Achievement Test performance scores prior to the onset of the study. Students in the implicit group attained significantly higher comprehension scores than did students in the explicit group. The results from the program sessions indicated no significant differences in reading comprehension between the implicit and explicit conditions, with the exception of the 6th session involving the reading and interpreting of graphic text. Students in the explicit group performed significantly better when reading and interpreting graphic text than those in the implicit group. No significant differences were evident between the two study conditions across the three summative tests. Upon completion of the study, the results from the Canadian Achievement Test indicated no significant differences in performance between the two study conditions. The findings from this study reveal the effectiveness of providing students with explicit strategy instruction when reading and responding to various forms of text. Modelling the appropriate reading comprehension strategies and test taking skills enabled students to apply the same thought processes to their own independent work. This form of instruction enabled students in the explicit group to improve in their abilities to comprehend and respond to text and therefore should be incorporated as an effective form of classroom teaching.

A Needs Assessment: Language Instruction Stakeholders Engaging in Project Based Learning Outside the Classroom for Effective Strategic Problem Solving

Abstract A noted benefit of Project Based Learning (PBL) as a teaching strategy is how it engages the student and enhances learning outcomes as a result of working through challenges intended to depict dilemmas outside the classroom. PBL has seldom been applied outside the parameters of the classroom curriculum. The current needs assessment carried out in this research project examined current practices of language instruction and International Administrative Professionals of both the private and public Language Industry. Participants responded to survey questions on their current administrative practices, strategies, and program characteristics. The study investigated the usefulness of a handbook on the procedure of assisting administrative service teams in language instruction settings to an engaged approach to PBL for student service issues. The diverse opinions, beliefs, and ideas, along with institutional policy, can provide beneficial framework ideas for future tools.

(A) BODIPY as a versatile fluorophore (B) Synthesis of PNAs via Staudinger reaction

(A) In recent years, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) fluorophores have attracted considerable interest due to their unique photochemical properties. However detailed studies on the stability of BODIPY and analogues under acidic and basic conditions have been lacking. Thus the stability of a series of BODIPY analogues in acidic (di- and trichloroacetic acid) and basic (aqueous ammonium hydroxide) conditions was investigated using 11B NMR spectroscopy. Among the analogues tested, 4,4-diphenyl BODIPY was the most stable under the conditions used in the experiments. It was found that reaction of 4,4-dimethoxy BODIPY with dichloroacetic acid gave mixed anhydride 4,4-bis(dichloroacetoxy) BODIPY in good yields. Treatment of the latter mixed anhydride with alcohols such as methanol and ethanol in the presence of a base afforded corresponding borate esters, whereas treatment with 1,2-diols such as ethylene glycol and catechol in the presence of a base gave corresponding cyclic borate esters. Furthermore treatment of 4,4-difluoro-8-methyl-BODIPY with secondary amines in dihalomethane resulted in carbon–carbon bond formation at the meso-methyl position of BODIPY via Mannich-type reactions. The resulting modified BODIPY fluorophores possess high fluorescent quantum yields. Five BODIPY analogues bearing potential ion-binding moieties were synthesized via this Mannich-type reaction. Among these, the BODIPY bearing an aza-18-crown-5 tether was found to be selective towards copper (II) ion, resulting in a large blue shift in absorption and sharp fluorescent quenching, whereas aza-15-crown-4 analogue was selected towards fluoride ion, leading to effective florescent quenching and blue shift. (B) Peptide nucleic acids (PNA), as mimics of natural nucleic acids, have been widely applied in molecular biology and biotechnology. Currently, the preparation of PNA oligomers is commonly achieved by a coupling reaction between carboxyl and amino groups in the presence of an activator. In this thesis attempts were made towards the synthesis of PNA through the Staudinger ligation reactions between C-terminal diphenylphosphinomethanethiol thioesters and N-terminal α-azido PNA building blocks.

The Effective Use of 21st-Century Learning iPad Applications in the Primary/Junior Literacy Classroom

The purpose of this major research project was to develop a practical tool in the form of a handbook that could facilitate educators’ effective use of technology in primary and junior classrooms. The main goal was to explore the use of iPad devices and applications in the literacy classroom. The study audited available free applications against set criteria and selected only those that promoted 21st-century learning. The researcher used such applications to develop literacy lessons that aligned with curriculum expectations and promoted 21st-century skills and traditional skills alike. The study also created assessment models to evaluate the use of iPads in student work and explored the benefits and limitations of technology usage in student learning.

Using Effective Teaching Strategies and Personality Type to Enhance the Mathematics Classroom: A Handbook for Intermediate Math Teachers

This project addressed the need for more insightful, current, and applicable resources for intermediate math teachers in Canadian classrooms. A need for a handbook in this division seemed warranted by a lack of government resource support. Throughout an extensive review of the literature, themes and topics for the handbook emerged. The handbook was designed to not only provide educators with examples of effective teaching strategies within the mathematics classroom but to also inform them about the ways in which their personal characteristics and personality type could affect their students and their own pedagogical practices. Three teaching professionals who had each taught in an intermediate math class within the past year evaluated the handbook. The feedback received from these educators was directly applied to the first draft of the handbook in order to make it more accessible and applicable to other math teachers. Although the handbook was written with teachers in mind, the language and format used throughout the manual also make it accessible to parents, tutors, preservice education students, and educational administrators. Essentially, any individual who is hoping to inspire and educate intermediate math students could make use of the content within the handbook.