Topology of Organometallic Radicals How does coordination with transition metals affect reactivity&stereoelectronic parameters of propargyl cation&radical?

Slides:

Advertisements

Similar presentations

Metabolism Collection of biochemical rxns within a cell Metabolic pathways –Sequence of rxns –Each step catalyzed by a different enzyme Enzymes of a pathway.

Advertisements

Enzyme Kinetic Zhi Hui.

Anion radical coupling. Plan  methods for the formation of aryl-aryl bonds  anionic cyclohydrogenation  history  mechanism  applications.

Oxidative Coupling Scott Dufour.

Green Oxidation Catalysts Synthesis of a catalyst for environmentally benign oxidation by N 2 O Addie Summitt and Megumi Fujita* Department of Chemistry,

© 2011 Pearson Education, Inc. 1 Organic Chemistry 6 th Edition Paula Yurkanis Bruice Chapter 20 More About Oxidation–Reduction Reactions.

Biology 107 Introduction to Metabolism II September 15, 2003.

Advanced Higher Chemistry Unit 1 Oxidation states of the transition metals.

Experiment 9 Preparation and Analysis of a Coordination Compound.

Lecture 14 APPLICATIONS IN ORGANIC SYNTHESIS Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Factors Affecting Enzyme Activity

The ammonium salt formation is reversible. Upon heating, a slower but thermodynamically more favorable reaction between the carboxylic acid and the amine.

MSE-536 Protein Interactions with Biomaterials Topics: Thermodynamics of Protein Adsorption Protein Structure Protein Transport and Adsorption Kinetics.

ENZYMES Enzymes lower the activation energy of reactions.

1 Single electron transfer reaction involving 1,3-dicarbonyl compounds and its synthetic applications Reporter: Jie Yu Oct. 31, 2009.

GROUP 1 COMPOUNDS – SYNTHESIS AND STRUCTURE Lithium reagents generally exhibit lower reactivity. This arises from lithium forming bonds with a greater.

Amide bond formation and peptide coupling Mgr. Juraj Dobiaš KOCH PRIF UK Ch. A. G. N., Montalbetti; V., Falque Tetrahedron 2005, 61, 10827–10852.

13-1 CHEM 102, Spring 2012, LA TECH CTH 328 9:30-10:45 am Instructor: Dr. Upali Siriwardane Office: CTH 311 Phone Office.

Chapter 21 The Radical Chemistry

CHAPTER 11 ELEMENTS OF ELECTROCHEMISTRY Introduction to Analytical Chemistry.

6-1 6 Copyright © 2000 by John Wiley & Sons, Inc. All rights reserved. Introduction to Organic Chemistry 2 ed William H. Brown.

1 Enzymes - Level Enzymes - Level I. Enzymes are proteins and have a 3D shape. II. Enzymes turn the food we eat into energy and unlock this energy.

Song jin July 10, 2010 Gong Group Meeting.

An Introduction to Metabolism.  Metabolism = Catabolism + Anabolism  Catabolic reactions are energy yielding They are involved in the breakdown of more-

Chapter 5 – Analysing Oxidants & Reductants Week 3, Lesson 1.

Energy, ATP, and Enzymes.

The goal: analyze complex enzymatic pathways How do you increase the specificity of enzyme detection?

Jean-Louis Brochu Department of Chemistry University of Ottawa

Friday, March 5 th. Quick Review Entropy vs enthalpy Gibbs free energy (ΔG) What reactions are likely to occur?

CHEE 323J.S. Parent1 Projected Trends in U.S. Liquid Fuels Demand With world oil prices in the range of USD/bbl, liquid fuel chemistry is the single.

Indium in Organic Synthesis Huang-Jianzhou

Lecture 11 CATALYSIS I. Hydrogenation and hydroelementation Alkenes Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or.

13-1 CHEM 102, Spring 2015, LA TECH Instructor: Dr. Upali Siriwardane Office: CTH 311 Phone Office Hours: M,W 8:00-9:30.

Characterization of E and Z-α-methylene γ-butyrolactones OBJECTIVE  The purpose of this study is to develop a new method for construction of the aryltetralignan.

Electrochemistry Ch. 18 Electrochemistry 18.1 Voltaic Cells.

1 SURVEY OF BIOCHEMISTRY Enzyme Catalysis. 2 Enzymatic Catalysis: Recap General Properties of Enzymes –6 Enzyme Classes –Substrate Specificity –Types.

Energy and Enzymes Chapter 6 Almost all energy for life is derived from the sun. Life requires energy.

Using curved arrows, propose a mechanism for this transformation:

Klein, Organic Chemistry 2e

In voltaic cells, oxidation takes place at the anode, yielding electrons that flow to the cathode, where reduction occurs. Section 1: Voltaic Cells K What.

Organic Chemistry Second Edition Chapter 11 David Klein

组会汇报文献汇报李满 04/15/2016.

CHEM 106/320: Fundamentals of Analytical Chemistry

Warm up Draw an example of a monosaccharide What type of macromolecule is this? Draw an example of a fatty acid What type of bonds hold together amino.

Efficiency in Synthesis

Presentations Tuesday, May 8th ~7-10pm

Bioreactors Engineering

-Bonded Cationic Ligands as Catalysts and Precursors

Figure Number: 24-01b Title: Figure 24.1(b)

Enzyme-Substrate Complex

Electrochemistry Chapter 17.

Chapter 5 – Analysing Oxidants & Reductants

Organ metallic Compounds

CONCEPT 3: ANALYZING CELL METABOLISM AND ENZYME FUNCTION (CH 8, AP LAB 2) Holtzclaw: “Metabolism” pg Campbell: Read pg , Look.

ENZYME Enzyme Reaction Energy of reaction Factors affect rate Other.

Chemistry of Life Enzymes

Tunable σ-Accepting, Z-Type Ligands for Organometallic Catalysis

Synthesis, Metal Ion Complexation, and Emission Studies of Naphthalimide Based Fluoroionophores Jeffrey E. Elbert, Department of Chemistry and Biochemistry,

Organic Reactions Enabled by Catalytically Active Metal–Metal Bonds

Water as the Preferred Solvent for Lewis Acid-Catalyzed Free Radical Polymerization and Initiation of Spontaneous 'Charge-Transfer' Polymerization H.K.

Development of Transition Metal Catalysts for

Presentation transcript:

Topology of Organometallic Radicals

How does coordination with transition metals affect reactivity&stereoelectronic parameters of propargyl cation&radical?

Alternative Strategies for Generation of Co2(CO)6 - Complexed Propargyl Radicals

Tetrahydrofuran-Mediated Generation and Stereoselective Coupling of Cobalt-Complexed Propargyl Radicals

THF: Synthetic Profile

Understanding THF-Mediated Radical Reaction: Hydride Ion Transfer versus Direct Single Electron Reduction

Mechanism of THF-Mediated Radical Reaction

Unorthodox Radical Chemistry

Spontaneous Generation of Cobalt- Complexed Propargyl Radicals

Tentative Mechanism of Spontaneous Reaction

The Effect of Temperature Upon Reaction Rate Gagik G. Melikyan, Boghos Mikailian, Ruth Sepanian, Pogban Toure. High-Temperature Reaction of a Co2(CO)6- Complexed Propargyl Cation. J. Organomet. Chem. 2009, 694,

Yield and d,l-Diastereoselectivity NOT Compromised Temperature TimeYield d,l:meso de 20°C11h80.0%94:688% 40°C100min93.0%94:688% 83°C6min88.0%92:884% 147°C1min84.0%90:1080%

High Temperature Reactions in Cobalt- Alkyne Chemistry

One-Step, Tf 2 O-Mediated Radical Reaction

Generation of Cobalt-Complexed Propargyl Cations under Acidic Conditions

Generation of Cobalt-Complexed Propargyl Cations under Acidic Conditions: An Alternative Approach

Generation of Cobalt-Complexed Propargyl Cations under Neutral Conditions

Expanding Reagent Base: Trifluoroacetic Anhydride vs Triflic Anhydride

Expanding Substrate Base of Spontaneous Radical Reaction

Can the New Method for Cation Generation Handle Acid- Sensitive Moieties?

How Free the Cobalt-Complexed Radicals Are?

New Avenue: Cross-Coupling Radical Reactions

Charge distribution and structural parameters derived from the PM3 and 3-21G* calculation.

Synopsis of Cross-Coupling Radical Reactions

Intramolecular Cyclizations: Topology

Intramolecular Radical Cyclizations: an Easy Access to 1,5-Cyclodecadiynes

Diastereoselectivity of Intramolecular Cyclizations

CH/pi-Coordination Leading to meso- Diastereomer

X-Ray Structures of 1,5-Alkadiynes & 1,5-Cycloalkadiynes

Synthetic Potential

Functional Group Tolerance

The Concept of Controlling the Concentration of Female Hormones

Can Radical Dimers Compete with Testosterone for an Enzymatic Site?

Aromatase Inhibitors (AIs): What is on the Market?

DNA Cleaving Agents of New Topology

Melikyan Research Group Spring 2009