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Articles 43831 - 43860 of 294412

Full-Text Articles in Physical Sciences and Mathematics

Development Of Est-Derived Simple Sequence Repeat (Ssr) Markers In Italian Ryegrass (Lolium Multiflorum Lam.), M. Hirata, Y. Miura, T. Takamizo, M. Fujimori Apr 2023

Development Of Est-Derived Simple Sequence Repeat (Ssr) Markers In Italian Ryegrass (Lolium Multiflorum Lam.), M. Hirata, Y. Miura, T. Takamizo, M. Fujimori

IGC Proceedings (1977-2023)

Italian ryegrass (IRG, Lolium multiflorum Lam.) is an important grass species used for agricultural purposes in Japan. Linkage maps in IRG have been constructed using molecular markers including RFLPs, AFLPs (Inoue et al., 2003) and genomic SSRs. The SSR marker is a useful tool for genome analysis because it is PCR-based with a relatively high level of polymorphism, co-dominantly expressed. The EST-SSR markers are expected to be more conserved and have a higher rate of transferability than genomic SSR markers (Scott et al., 2000), and the gene functions of ESTs may be predicted. Ikeda et al. (2004) …


Investigations Of The Effects Of Mutations In Inscuteable Mediated Pins-Mud Complex And Par Complex Functions In Drosophila Neuroblast, Ryan Liu Apr 2023

Investigations Of The Effects Of Mutations In Inscuteable Mediated Pins-Mud Complex And Par Complex Functions In Drosophila Neuroblast, Ryan Liu

Research & Creative Achievement Day

Drosophila melanogaster central brain neuroblasts asymmetrically segregate proteins along the cell's apical-basal axil. Divisions along abnormal orientations or the complete failure to divide asymmetrically may result in overgrowth phenotypes. Neuroblastoma, one of the deadliest solid tumor diseases with extremely poor survival rate for late stages, is an example of this dysregulation. The protein Inscuteable (Insc) was previously found to bind with the protein Partner of Inscuteable (Pins; mPins or LGN in mammals), a receptor-independent G-protein activator, which is a subunit of the Pins-Gαi complex. The combined complex recruits Dlg to ensure correct spindle attachment on the cortex of the cell, …


A Closer Look At The Death Penalty In The United States, Anna L. Cardell Apr 2023

A Closer Look At The Death Penalty In The United States, Anna L. Cardell

Research & Creative Achievement Day

The death penalty has always been a source of contention towards most people in the United States – some agree with it, some do not. No matter one's opinion on whether it should be allowed, this poster presentation will give an in-depth analysis and present various visualizations of information regarding the convicted felons that have been sentenced to capital punishment in the United States from 1976-2016. Variables such as gender, age, and race will be explored to create some insight on some of the most infamous killers in United States history. Though looking at the demographics of these individuals and …


Validation Of Computational Methods For The Tautomerism Of Thiourea Dioxide, Mckenna Lund Apr 2023

Validation Of Computational Methods For The Tautomerism Of Thiourea Dioxide, Mckenna Lund

Research & Creative Achievement Day

In solution, thiourea dioxide exists in an equilibrium between its dioxide and sulfinic acid forms. This tautomeric relationship, as they all are, is substantially influenced by the solvent's polarity and hydrogen bonding capabilities. More well-known systems, e.g., acetylacetone, have been extensively studied in this regard, while thiourea dioxide's equilibrium has not. We have initiated a hybrid computational-spectroscopic investigation of this system utilizing low-cost Hartree-Fock methods with the 3–21G, 3–21+G, 3–21G*, 3–21+G*, MINI, MIDI, SBKJC and HW basis sets. Beyond gas phase calculations, both tautomeric forms were modeled using the C-PCM implicit solvent model for water and toluene. Obtained modeling results …


Improvement Of Native Perennial Forage Plants For Sustainability Of Mediterranean Farming Systems, F. Lelièvre, Florence Volaire Apr 2023

Improvement Of Native Perennial Forage Plants For Sustainability Of Mediterranean Farming Systems, F. Lelièvre, Florence Volaire

IGC Proceedings (1977-2023)

The amount of water available to agriculture in the Mediterranean is declining because of increasing population pressure and greater incidence of drought. Therefore, the efficiency of the use of water for agricultural production must be maximized and, in this context, perennial forage species have a number of advantages in comparison to the predominantly-used annuals. They can utilize water throughout the whole year besides being able to halt rangeland degradation, restore soil fertility and enhance forage production, thereby contributing to greater sustainability of rain-fed agricultural systems in the southern European Union and North Africa. Despite these advantages, the small size of …


The Potential For Summer-Dormant Perennial Grasses In Mediterranean And Semi-Arid Pastures, F. Lelièvre, Florence Volaire, P. Chapon, M. Norton Apr 2023

The Potential For Summer-Dormant Perennial Grasses In Mediterranean And Semi-Arid Pastures, F. Lelièvre, Florence Volaire, P. Chapon, M. Norton

IGC Proceedings (1977-2023)

In rain-fed Mediterranean and semi-arid areas, herbage production of perennial grasses depends on their ability to grow efficiently during the rainy seasons and to persist over the dry summer. A key survival strategy in these harsh conditions is summer dormancy (Volaire, 2002). Within the species Dactylis glomerata L., two cultivars (cvs.), contrasting in this trait, were compared in order to analyse their suitability in terms of yield and survival in these environments.


Future Directions In The Molecular Breeding Of Forage And Turf, G. C. Spangenberg, J. W. Forster, D. Edwards, U. John, A. Mouradov, M. Emmerling, J. Batley, S. Felitti, N. O. I. Cogan, K. F. Smith, M. P. Dobrowolski Apr 2023

Future Directions In The Molecular Breeding Of Forage And Turf, G. C. Spangenberg, J. W. Forster, D. Edwards, U. John, A. Mouradov, M. Emmerling, J. Batley, S. Felitti, N. O. I. Cogan, K. F. Smith, M. P. Dobrowolski

IGC Proceedings (1977-2023)

Key points

  1. Molecular breeding of forage and turf plants and their endosymbionts has entered the post-genomic era with a large amount of structural genomics information and genomic resources available for key forage and turf species and relevant model systems.
  2. A primary future challenge is the conversion of this information into useful functional knowledge for the development of molecular breeding technologies and products that address a range of high impact outcome scenarios in forage and turf.
  3. High-throughput approaches for spatial and temporal analysis, from genome to phenome, and the respective data integration in a systems biology context will be critical for …


Crown Rust Resistance In Transgenic Italian Ryegrass (L. Multiflorum) Expressing A Rice Chitinase Gene And Crosses With Cytoplasmic Male Sterile Hybrid Ryegrass, W. Takahashi, M. Fujimori, Y. Miura, T. Komatsu, S. Sugita, A. Arakawa, Y. Nishizawa, H. Sato, Y. Mano, T. Hibi, T. Takamizo Apr 2023

Crown Rust Resistance In Transgenic Italian Ryegrass (L. Multiflorum) Expressing A Rice Chitinase Gene And Crosses With Cytoplasmic Male Sterile Hybrid Ryegrass, W. Takahashi, M. Fujimori, Y. Miura, T. Komatsu, S. Sugita, A. Arakawa, Y. Nishizawa, H. Sato, Y. Mano, T. Hibi, T. Takamizo

IGC Proceedings (1977-2023)

Italian ryegrass (Lolium multiflorum Lam.) is one of the most important forage grasses in the temperate region. In ryegrasses, crown rust (Puccinia coronata) is the most serious foliar fungal disease and brings about a reduction of herbage yield and loss of palatability to grass-eating domestic animals. In this study, we tried to increase tolerance to the pathogen by introducing a rice chitinase gene using particle bombardment.


Genetic And Molecular Characterization Of Temperate And Tropical Forage Maize Inbred Lines, B. Alarcón-Zúñiga, E. Valadez-Moctezuma, T. Cervantes-Martinez, T. Cervantes-Santana, M. Mendoza‐Rodriguez Apr 2023

Genetic And Molecular Characterization Of Temperate And Tropical Forage Maize Inbred Lines, B. Alarcón-Zúñiga, E. Valadez-Moctezuma, T. Cervantes-Martinez, T. Cervantes-Santana, M. Mendoza‐Rodriguez

IGC Proceedings (1977-2023)

Livestock feeding in the Central highland of Mexico is based on harvest, grazing and annual forage conservation, with forage maize being the most important silage crop (Alarcón, 1995). Even though forage maize is extensively bred in Europe, USA and Asia since the 1900’s, this started in Mexico only in the 1960’s, and little is known about genetic diversity in both agronomic and nutritive value traits. Our breeding program goals are to analyze combining ability of biomass and quality predictors and to study the genetic relationship of inbred lines between lowland tropical and temperate races from Mesa Central, by genetic and …


The Use Of Molecular Markers In Genetic Variability Analysis Of A Collection Of Dactylis Glomerata L., R. Costa, G. Pereira, C. Vicente, M. M. Tavares De Sousa Apr 2023

The Use Of Molecular Markers In Genetic Variability Analysis Of A Collection Of Dactylis Glomerata L., R. Costa, G. Pereira, C. Vicente, M. M. Tavares De Sousa

IGC Proceedings (1977-2023)

Dactylis glomerata L. is one of the three most used perennial grasses in Europe (jointly with Lolium perenne and Festuca arundinacea). The main qualities of Dactylis glomerata are high productivity in pure cultures, high level of proteins and tolerance to drought, cold and shade (Mousset & Chosson, 1986). In the last ten years, techniques that allow direct discrimination at the DNA level have encouraged the study of the genetic variability within cultivated populations as well as identification of the diversity available in germplasm banks. DNA polymorphisms have been shown to be efficient in the identification of genetic variability in …


Molecular Characterization And Tissue Culture Regeneration Ability Of The Usa Arachis Pintoi (Krap. And Greg.) Germplasm Collection, M. A. Carvalho, K. H. Quesenberry, M. Gallo-Meagher Apr 2023

Molecular Characterization And Tissue Culture Regeneration Ability Of The Usa Arachis Pintoi (Krap. And Greg.) Germplasm Collection, M. A. Carvalho, K. H. Quesenberry, M. Gallo-Meagher

IGC Proceedings (1977-2023)

Arachis pintoi Krap. and Greg. is a herbaceous, perennial legume, exclusively native to Brazil. It is considered a multiple use legume, being grown for forage; ground cover in fruits orchards, forest, and low tillage systems; erosion control; and ornamental purposes. Although several cultivars have been released in different countries, little is known about the genetic diversity of the germplasm stored in world genebanks. Our objective was to characterize and evaluate the genetic diversity of the germplasm of 35 accessions of Arachis pintoi at molecular level using RAPD markers. Concurrently, two tissue culture protocols were evaluated for their organogenesis ability. Further, …


Genetic And Phenotypic Diversity Of Swiss Red Clover Landraces, D. Herrmann, B. Boller, F. Widmer, R. Kölliker Apr 2023

Genetic And Phenotypic Diversity Of Swiss Red Clover Landraces, D. Herrmann, B. Boller, F. Widmer, R. Kölliker

IGC Proceedings (1977-2023)

Mattenklee landraces are persistent and locally adapted Swiss red clover populations. About 100 populations are preserved and may represent a significant yet poorly characterised genetic resource for temperate regions. Genetic characterisation is important in order to improve cultivars, manage genetic resources and to maintain or restore biodiversity. The objectives of this study were to analyse genetic diversity, investigate potential ancestry and to elucidate the congruence of phenotypic and genetic structure of Mattenklee landraces.


Improving The Utilisation Of Germplasm Of Trifolium Spumosum L. By The Development Of A Core Collection Using Ecogeographical And Molecular Techniques, K. Ghamkhar, R. Snowball, S. J. Bennett Apr 2023

Improving The Utilisation Of Germplasm Of Trifolium Spumosum L. By The Development Of A Core Collection Using Ecogeographical And Molecular Techniques, K. Ghamkhar, R. Snowball, S. J. Bennett

IGC Proceedings (1977-2023)

A core collection is a sub-set encompassing more than 70% of the variability of all accessions held in a collection (Brown, 1995). The development of one for Trifolium spumosum (bladder clover) could assist in future development of the cultivar within southern Australia. The aim of this work is to develop a core collection of Trifolium spumosum as a model for other pasture legume species using molecular and ecogeographical data.


Applying Bioactive Glass Beads For Long-Term Drug Delivery, Marie O. Sykes, Rashi Sharma Apr 2023

Applying Bioactive Glass Beads For Long-Term Drug Delivery, Marie O. Sykes, Rashi Sharma

Physics and Astronomy Presentations

Bioactive glass beads have been used to distribute medicine over extended periods of time in limited uses. They can be engineered to have a porous and hollow structure, and using Mo-Sci's OL-GL 1756b (1756b), the fundamental notion of dosage distribution can be tested in preparation to design the optimal glass for medicine distribution. A few key factors in this is how long does it take the liquid to release from the beads, how do the beads decay, and how well the glass can bond to human tissue. This research demonstrates the capacities of the 1756b type as a promising start …


Ecomves: Enhancing Comves Using Data Piggybacking For Resource Discovery At The Network Edge, Sanzida Hoque Apr 2023

Ecomves: Enhancing Comves Using Data Piggybacking For Resource Discovery At The Network Edge, Sanzida Hoque

Theses

Over the past few years, Augmented Reality (AR) and Virtual Reality (VR) have emerged as highly popular technologies that demand rapid and efficient processing of data with low latency and high bandwidth, in order to enable seamless real-time interaction between users and the virtual environment. This presents challenges for network infrastructure design, which can be addressed through edge computing. However, edge computing also presents challenges, such as selecting the appropriate edge server for computing tasks in dynamic networks with rapidly changing resource availability. Named Data Networking (NDN) is a potential future Internet architecture that could provide a balanced distribution of …


Chemical Analysis Of Morris Water Pollutants Via Electrochemical Detection Methods, Emily Miller Apr 2023

Chemical Analysis Of Morris Water Pollutants Via Electrochemical Detection Methods, Emily Miller

Undergraduate Research Symposium 2023

In small towns like Morris that are surrounded by agriculture, there’s an increased likelihood of contaminants to be present in the water. These commonly include heavy metals and pesticides which, in high enough dosages or prolonged exposure, can quickly become poisonous and harmful with lasting effects for both plants and humans. Throughout our research we have been analyzing the presence, if any, of lead, copper and cadmium as well as the common pesticides atrazine and mesotrione in the water throughout Morris. We look at a variety of samples coming from melted snow (collected throughout Nov. 2022–Apr. 2023), drinking water, and …


Nviz: Unraveling Neural Networks Through Visualization, Kevin Hoffman Apr 2023

Nviz: Unraveling Neural Networks Through Visualization, Kevin Hoffman

Mathematics, Computer Science & Statistics Presentations

The growing utility of artificial intelligence (AI) is attributed to the development of neural networks. These networks are a class of models that make predictions based on previously observed data. While the inferential power of neural networks is great, the ability to explain their results is difficult because the underlying model is automatically generated. The AI community commonly refers to neural networks as black boxes because the patterns they learn from the data are not easily understood. This project aims to improve the visibility of patterns that neural networks identify in data. Through an interactive web application, NVIZ affords the …


R Text Analysis For Adam Smith Cie Selected Works, Charlotte Grahame Apr 2023

R Text Analysis For Adam Smith Cie Selected Works, Charlotte Grahame

Mathematics, Computer Science & Statistics Presentations

Text mining and text analysis is a way of understanding text documents using r coding that is more frequently used for numbered data. It helps with understanding portions of the text and drawing conclusions from there. This research looks specifically at the Adam Smith required documents that are used in the CIE course designated for freshmen. It looks at sentiments of the documents, including word sentiment, sentence sentiment, page and overall document sentiment as well. It provides visuals of word clouds to portray word frequency, tf-idf (which is explained in the presentation) and bigram analysis.


Cie Text Analysis: Narrative Of The Life Of Frederick Douglass, The Declaration Of Independence, And The Declaration Of Sentiments, Arianna Knipe Apr 2023

Cie Text Analysis: Narrative Of The Life Of Frederick Douglass, The Declaration Of Independence, And The Declaration Of Sentiments, Arianna Knipe

Mathematics, Computer Science & Statistics Presentations

Our STAT-451 class has worked with analyzing the words from CIE texts and assigning them to a sentiment or feeling and comparing them with one another using RStudio. This project analyzes texts from three sources: The Narrative of the Life of Frederick Douglass, The Declaration of Independence and the Declaration of Sentiments.


Translation Of: Sur Des Familles D’Hypersurfaces Isoparamétriques Des Espaces Sphériques À 5 Et À 9 Dimensions, Revista Univ. Tucuman, Serie A, 1 (1940), 5–22, By Elie Cartan, Thomas E. Cecil Apr 2023

Translation Of: Sur Des Familles D’Hypersurfaces Isoparamétriques Des Espaces Sphériques À 5 Et À 9 Dimensions, Revista Univ. Tucuman, Serie A, 1 (1940), 5–22, By Elie Cartan, Thomas E. Cecil

Mathematics and Computer Science Department Faculty Scholarship

English title: On Families of Isoparametric Hypersurfaces in Spherical Spaces of 5 and 9 Dimensions

This is an English translation of the article "Sur des familles d'hypersurfaces isoparamétriques des espaces sphériques à 5 et à 9 dimensions" which was originally published in Revista Univ. Tucuman, Serie A, 1, pp. 5-22 (1940), by Élie Cartan.

A note from Thomas E. Cecil, translator: This is an unofficial translation of the original paper which was written in French. All references should be made to the original paper.

Mathematics Subject Classification Numbers: 53B25, 53C40, 53C42


"In The Beginning, God Created Atoms", Samiya L. Henry Apr 2023

"In The Beginning, God Created Atoms", Samiya L. Henry

Undergraduate Research and Scholarship Symposium

Genesis 1:1 states “In the beginning, God created the heavens and the earth.” This is the defining statement in the Bible and acts as the foundation of creation and God’s power in the Christian faith. On the other hand, many scientists believe the Big Bang Theory and the discoveries made in other fields of science solely define the creation of the universe and explain life as we know it, also disproving the Christian creation story and the overall existence of God. However, the exact opposite is true; God is science.

Alone, neither of these concepts (faith and science) fully solve …


Loss Scaling And Step Size In Deep Learning Optimizatio, Nora Alosily Apr 2023

Loss Scaling And Step Size In Deep Learning Optimizatio, Nora Alosily

Dissertations

Deep learning training consumes ever-increasing time and resources, and that is
due to the complexity of the model, the number of updates taken to reach good
results, and both the amount and dimensionality of the data. In this dissertation,
we will focus on making the process of training more efficient by focusing on the
step size to reduce the number of computations for parameters in each update.
We achieved our objective in two new ways: we use loss scaling as a proxy for
the learning rate, and we use learnable layer-wise optimizers. Although our work
is perhaps not the first …


Volume 14, Ireland Seagle, Dalton C. Whitby, Cassandra Poole, Rachel Cannon, Heidi Parker-Combes, Devon G. Shifflett, Antonio Harvey Apr 2023

Volume 14, Ireland Seagle, Dalton C. Whitby, Cassandra Poole, Rachel Cannon, Heidi Parker-Combes, Devon G. Shifflett, Antonio Harvey

Incite: The Journal of Undergraduate Scholarship

Table of Contents:

  • Introduction: Dr. Amorette Barber
  • From the Editor: Dr. Larissa "Kat" Tracy
  • From the Designers: Rachel English, Rachel Hanson
  • Hungry Like the Wolf: The Wolf as Metaphor in Paramount Network’s Yellowstone: Ireland Seagle
  • “Floating Cities”: Illustrating the Commercial and Conservation Conflict of Alaskan Cruise Ship Tourism: Dalton C. Whitby
  • What Can You Do When Your Genes are the Enemy? Current Applications of Gene Manipulation and the Associated Ethical Considerations: Cassandra Poole
  • La doble cara: un tema romántico en las obras de Larra y Hawthorne: Rachel Cannon
  • Resolving a Conflict: How to …


Building Credibility, Trust, And Safety On Video-Sharing Platforms, Shuo Niu, Zhicong Lu, Amy X. Zhang, Jie Cai, Carla F. Griggio, Hendrick Heuer Apr 2023

Building Credibility, Trust, And Safety On Video-Sharing Platforms, Shuo Niu, Zhicong Lu, Amy X. Zhang, Jie Cai, Carla F. Griggio, Hendrick Heuer

Computer Science

Video-sharing platforms (VSPs) such as YouTube, TikTok, and Twitch attract millions of users and have become influential information sources, especially among the young generation. Video creators and live streamers make videos to engage viewers and form online communities. VSP celebrities obtain monetary benefits through monetization programs and affiliated markets. However, there is a growing concern that user-generated videos are becoming a vehicle for spreading misinformation and controversial content. Creators may make inappropriate content for attention and financial benefits. Some other creators also face harassment and attack. This workshop seeks to bring together a group of HCI scholars to brainstorm technical …


Mth 125 - Modeling With Exponential Functions, Stivi Manoku Apr 2023

Mth 125 - Modeling With Exponential Functions, Stivi Manoku

Open Educational Resources

The file includes a variety of problems that emphasize the importance of modeling exponential growth and/or radioactive decay. Through different exercises and problems, the assignment goal is to improve their comprehension of exponential functions and hone their problem-solving abilities.


A Large-Scale Survey Of Brown Dwarf Atmospheres, Savanah Kay Turner Apr 2023

A Large-Scale Survey Of Brown Dwarf Atmospheres, Savanah Kay Turner

Theses and Dissertations

Brown dwarfs are substellar objects that fall in-between the smallest stars and largest planets in size and temperature. Due to their relatively cool temperatures, the atmospheres of these 'failed stars' have been shown to exhibit interesting properties such as iron, silicate, and salt clouds. Theoretical atmospheric models based on known physics and chemistry can be used as tools to interpret and understand our observations of brown dwarfs. I have fit archival and new infrared spectra of over 300 brown dwarfs with atmospheric models. Using the parameters of the best-fit models as estimates for the physical properties of the brown dwarfs …


A Multi-Site Randomized Trial Of A Clinical Decision Support Intervention To Improve Problem List Completeness, Angela Ai, Raja Arul Cholan, Akshay Desai, Miguel Divo, David A Dorr, Thu-Trang Hickman, Salman Hussain, Shari Just, Brian Koh, Stuart Lipsitz, Dustin Mcevoy, Trent Rosenbloom, Elise Russo, David Yut-Chee Ting, Asli Weitkamp, Dean F Sittig Apr 2023

A Multi-Site Randomized Trial Of A Clinical Decision Support Intervention To Improve Problem List Completeness, Angela Ai, Raja Arul Cholan, Akshay Desai, Miguel Divo, David A Dorr, Thu-Trang Hickman, Salman Hussain, Shari Just, Brian Koh, Stuart Lipsitz, Dustin Mcevoy, Trent Rosenbloom, Elise Russo, David Yut-Chee Ting, Asli Weitkamp, Dean F Sittig

Faculty, Staff and Student Publications

OBJECTIVE: To improve problem list documentation and care quality.

MATERIALS AND METHODS: We developed algorithms to infer clinical problems a patient has that are not recorded on the coded problem list using structured data in the electronic health record (EHR) for 12 clinically significant heart, lung, and blood diseases. We also developed a clinical decision support (CDS) intervention which suggests adding missing problems to the problem list. We evaluated the intervention at 4 diverse healthcare systems using 3 different EHRs in a randomized trial using 3 predetermined outcome measures: alert acceptance, problem addition, and National Committee for Quality Assurance Healthcare …


Rethinking" Risk" In Algorithmic Systems Through A Computational Narrative Analysis Of Casenotes In Child-Welfare, Devansh Saxena, Erina Seh-Young Moon, Aryan Chaurasia, Yixin Guan, Shion Guha Apr 2023

Rethinking" Risk" In Algorithmic Systems Through A Computational Narrative Analysis Of Casenotes In Child-Welfare, Devansh Saxena, Erina Seh-Young Moon, Aryan Chaurasia, Yixin Guan, Shion Guha

Health Services and Informatics Research

No abstract provided.


Offsets And The Path To Carbon Neutrality In Higher Education And Study Abroad, Paul Sylvester, Michael A. Di Giovine, Bradley Flamm Apr 2023

Offsets And The Path To Carbon Neutrality In Higher Education And Study Abroad, Paul Sylvester, Michael A. Di Giovine, Bradley Flamm

Sustainability Research & Practice Seminar Presentations

Professors Paul Sylvester, Early & Middle Grades Education, and Michael Di Giovine, Anthropology, in conversation with Bradley Flamm - Offsets and the Path to Carbon Neutrality in Higher Education and Study Abroad


Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker Apr 2023

Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker

Dartmouth College Ph.D Dissertations

Methylation of P-stereogenic phosphiranes Mes*PCH2CH(R) (Mes* = 2,4,6-(t-Bu)3C6H2, R = Me, Ph) with MeOTf gave P-stereogenic phosphiranium cations; [Mes*P(Me)CH2CH(Ph)][OTf] underwent syn-anti isomerization via P-epimerization. Mechanistic studies suggested ring opening gave a hyperconjugation-stabilized carbocation in which pyramidal inversion at P was promoted by s-interaction with the pendant cation. Attempted phosphirane protonation with HOTf resulted in ring opening and C-H activation of an o-t-Bu group to give phospholanium cations. Treatment of [Mes*P(Me)CH2CH(Ph)][OTf] with LiPPh2 gave bis(phosphino)ethanes. Copper- catalyzed P-alkylation of the secondary phosphine PHPh(Mes*) with benzyl bromides gave P-stereogenic tertiary phosphines with a supermesityl substituent.