Aspects of Mechanism and Organometallic Chemistry

ISBN-13: 9781468433951 / Angielski / Miękka / 2012 / 347 str.

J. H. Brewster

Opis

In May of 1978, several hundred of the friends, colleagues and former students of Professor Herbert C. Brown gathered on the campus of Purdue University to note his formal retirement, to honor him for his past contributions to chemistry and to wish him continued success in research. It was a time of reunion and recollection, a time for looking back and giving recognition to a lifetime of accomplishment. There was the ceremony of a banquet, presided over with inimitable wit by Professor Derek Davenport, and the dedication of the Herbert C. Brown Archives, with addresses by Dr. Alfred Bader, of Aldrich Chemicals, and Dr. Alan Schriesheim, of Exxon. There was the publi cation of a book of the personal reminiscences of students and post doctoral colleagues - "Remembering HCB." But it was also a time for looking at the present and into the future with a set of scien tific lectures, mainly by former students or associates, who des cribed their current or projected research activities. That is what this book is about. The papers, some of which are expanded versions of the lectures, fall into two broad groups - some deal with the interplay of struc ture and mechanism, the others deal with the use of organometallics in synthesis. It is, perhaps, no accident that these are the two main areas of H. C. Brown's research interest."

Spis treści

The Mechanistic Probe of Increasing Electron Demand in the Study of Solvolytic Reactions.- Arylalkyl, Arylcycloalkyl, and Arylpolycycloalkyl Systems.- Neighboring Group Effects.- ?-Conjugation.- ?-Participation.- ?- and ??-Conjugation.- ??-Participation.- ?-Participation/Bridging/etc.- Charge and Spin Derealization to the Trifluoromethyl Group.- Reaction Chemistry.- Physical and Spectroscopic Properties.- Molecular and Conformational Equilibria Studied by Electron Spin Resonance Spectroscopy.- Ion-Pair Formation for 1,2-Semidiones.- Use of the Semidione Spin Label to Study Conformational Equilibria.- Valence Isomerization of 1,2-Semidiones.- Sigmatropic Rearrangements Followed by the Observation of 1,2-Semidiones.- Valence Isomerization of 1,4-Semidiones.- Effects of Steric Strain on the Preparation, Stability, and Reactions of Aryl Anions and Amines.- Copper(II)-Induced Oxygenolysis of o-Benzoquinones, Catechols, and Phenols: The Active Copper(II)-Species, Role of Cupric Chloride and the General Question of Activation of Molecular Oxygen by Dioxygenases.- Copper(I) as a Catalyst for “Activation” of Molecular Oxygen.- Does Oxidation of Catechol to cis,cis-Muconic Acid Monomethyl Ester Require Molecular Oxygen?.- Nature of the Active Copper(Il)-Species in the “Cu-Reagent”.- Reaction of Cupric Methoxide/Water in Pyridine with Catechols and o-Benzoquinones 151.- Mechanism of the Cleavage of Catechol with “Cu-Reagent”.- On the Question of Activation of Molecular Oxygen by Monooxygenases and Dioxygenases.- Stereochemistry of the SE2 Bromine Cleavage of Tetraalkyltin Compounds in Carbon Tetrachloride and Methanol Solvents.- Selective Reductions Using Metal Hydrides.- Radionuclide Incorporation via Organoboranes.- Asymmetric Synthesis via Boranes: Chiral Allenic Boranes and Trialkylborane Reducing Agents.- The Conversion of Propargyl Acetates into Allenes and Acetylenes.- Trialkylborane Reducing Agents.- The Versatile Alkenylalanes and Alkenylboranes.- New Applications of Organomercury, -Palladium, and -Rhodium Compounds in Organic Synthesis.- Selective Carbon — Carbon Bond Formation via Transition Metal Catalysis: Is Nickel or Palladium Better Than Copper?.- The Ni-Catalyzed Reaction of (E)-l-Alkenylalanes with Aryl Halides.- The Pd-Catalyzed Alkenyl-Alkenyl Cross-Coupling Reaction.- Pd-Catalyzed Alkynyl-Aryl Cross Coupling — Comparison of Various Metals (M2) in the Organometallic Reagents (R2M2).- Scope of the Pd-Catalyzed Cross Coupling Involving Alkynyl Reagents.- Unsymmetrical Biaryls.- The Ni- and Pd-Catalyzed Cross-Coupling Reaction of (E)-1-Alkenylzirconium Derivatives.- Double-Metal-Catalyzed Cross Coupling — A Stereoselective Synthesis of Trisubstituted Olefins via Zirconium-Catalyzed Carboalumination.- A Brief Survey of the Ni- and Pd-Promoted Cross Coupling with sp3-Hybridized Reagents.- Herbert C. Brown — A Biographical Note.- About the Authors Who Were Associated with Professor Brown.- Subject Inde.