A. Loupy, B.Tchoubar. Salt Effects in Organic and Organometallic Chemistry

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1 A. Loupy, B.Tchoubar Salt Effects in Organic and Organometallic Chemistry

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3 1 Introduction - Classification of Specific Salt Effects Specific Salt Effects Involving the Salt's Lewis Acid or Base Character Salt Effects Arising from Exchange Reactions between Two Ion Pairs Salt Effects Connected with the Position of Ionic Dissociation Equilibria Specific Salt Effects Affecting the Structure of the Activated Complex i n the Transition State: Effect on the Stereo- and Regioselectivities Salt Effects Arising from Specific Associations with Protic Solvent s (Drying Effect) 6 References 8 2 Effects of Salts on the Rates of Single Bond Cleavage Reactions Specific Salt Effects Concerning the Heterolytic Cleavage of C-X Bonds Ionization of C-X Bonds Electrophilic assistance Nucleophilic assistance by salts - effects of anions Unimolcular Solvolysis Reactions (S N 1, E 1) Common ion mass effect "Normal" and "special" salt effects Retardation by the drying salt effect : S N1 reactions in mixed solvents Specific Salt Effects in Bimolecular Nucleophilic Reactions SN2 Reactions Brought About by Anionic Nucleophiles [Scheme (2-23)] Effect of the cation accompanying the anionic nucleophile ; ionic association or complexation of the electrophile Salt effects in SN2 reactions involving hard anionic reactants Salt effects in SN2 reactions involving soft anionic reactants SN2 Reactions Involving Electrically Neutral Nucleophiles Effect according to the nature of the salt anion The case of alkali metal fluorides Use of tetraalkylammonium fluorides Use of fluorides on solid mineral supports Other Cases of Heterolytic C-X Bond Cleavage Aromatic nucleophilic substitutions (SN Ar) Elimination reactions Nucleophilic Reactions with a Hydrogen Atom Reactive Site Cation Effects on C-H Bond Ionization caused by a Base Be C-H Bond Ionization Caused by Alkali Metal Fluorides 4 6 References 47

4 3 Effects of Salts on Rates of Addition Reactions to Multiple Bonds Anionic Nucleophilic Addition (AdN) to )C=O and Similar Bonds Effect of the Cation Introduced with the Anionic Reagent: Carbonyl Complexation or Ionic Association Carbonyl complexation : )C=O. M Ionic association Nu M Cation effects in AN. C=O reactions Types of Salt Effects in AN C=0 Reactions Effects due to added salt cations : carbonyl complexation or associatio n with the reactant Drying effects in protic media Salt Effects in Alkaline Ester Hydrolysis Aliphatic esters Aromatic esters The case of phenyl acetate Explanation in terms of frontier orbitals Examples of Salt Effects in AN C=0 Reactions Positive salt effects,..., Negative salt effects......_. _ Catalysis by trityl perchlorate AN C=0 Reactions Caused by Electrically Neutral Reagents Case of Other Unsaturated Compounds Having Electrophilic Character : Nucleophilic Addition to Nitriles Double Activation : Bifunctional Catalysis The Salt Taking Part as one of the Components in Double Activation As an electrophilic catalyst by means of M As nucleophilic catalyst by means of X _ The Salt Taking Part as a Bifunctional Catalyst Addition Reactions to C=C Double Bonds General Points : Substituent Effects and Types of Addition Donor substituent effects Withdrawing substituent effects Particular case of C=C double bond a to C= Electrophilic Addition (AdE) Acceleration resulting from the cation effect Acceleration brought about by the anion Acceleration of olefin oxidation by thallic salts in aqueous media throug h salt drying effects Aromatic Electrophilic Substitution Anisole acylation - : : ~,_ Mercuration of benzene ; salt drying effects Nucleophilic Addition to Double Bonds a to C= Accelerating effects due to the cation Inhibiting effects due tothe cation Salt effects 94

5 3.3.5 Particular Case of Halogen Addition to C=C-C=0 Conjugated Systems 9 5 References Effects of Salts on Reaction Orientation (Regioselectivity) Reactant Organization in the Vicinity of the Cation Macrocycle Synthesis : the "Template Effect" Synthesis of macrocycles in basic media Acid catalyzed macrocycle synthesis Effects of Salts on Intramolecular Cyclizations "Intramolecular self-solvation" effect Synthesis of benzo-18-crown Effect of Salts on Metallation Regioselectivity Effects of Salts on Regioselectivity of Anionic Reactions Effects involving Electrophilic Reactants Epoxide ring opening I3-Elimination reactions Reactions involving carbonyl compounds Effects Arising from the Nucleophilic Reagen t (Case of Mesomeric Anions) Effect of salts on the O/C ratio in an aprotic solvent Effect of salts on the O/C ratio in protic solvents Effect of salts on the O/C ratio in the case of aryloxy anions Effects of salts on the regioselectivity of alkylation of oximate s ()C=N-O Mm) Effects of salts on the ambident reactivity of aminoacid s (0/N alkylation ratio) The case of allylic carbanions a to SPh Effects of Salts on the Nature and Distribution of AdE2 Reactio n Products References Effects of Salts on Reaction Stereochemistry Effects Concerning the Electrophilic Reactant Bimolecular Nucleophilic Substitutions Effects at carbon Effects at silicon Effects at germanium Effects at phosphorus Ring-opening of Epoxides I3-Elimination (Syn vs. Anti Elimination) Reactions of Addition to Carbonyl Compounds Stereochemistry of additions to cyclic ketones Stereochemistry of aldol condensations Stereochemistry of the Wittig-reaction 159

6 Salt effects in asymmetric synthesis Nucleophilic Addition to Double Binds Conjugated with Electron With - drawing Groups Stereochemistry of Michael-type reactions Michael-type asymmetric synthesis Salt effects in asymmetric Michael reactions Salt Effects on the Steric Course of Nucleophilic Addition of Halogens Effects on the Anionic Nucleophilic Reactant C-Alkylation of Carbanionic Species Influence of association between the carbanion and its Mu counterion Role of the cation in the alkylation of carbanionic species a to a sulfoxid e group; salt effects Role of the cation in asymmetric alkylations a-alkylation of ketones Alkylation of Enolates of ß-Dicarbonyl Compounds Electrophilic Additions : Effects of Salts on Stereochemistry Salt Effects on the Steric Course of the Favorskii Rearrangement Case of a-haloketones Without a Mobile a' Hydrogen Case of a-haloketones with a Mobile a' Hydrogen Medium Effects on the Stereochemistry of Enolate Ketonizatio n (Protonation) Dissociating Protic Medium ; Effect of ph Cation Effects on Ketonization Stereochemistry in Inert Solvents 202 References Specific Effects of Salts on Equilibria Concepts of Activity and Activity Coefficients. Their Significance in Equilibria Specific Effects of Salts on Equilibria Preceding the Slow Step of Various Reactions Some Examples Illustrating the Effects of Salts on Uncatalyzed Pre - Equilibrated Reactions Salt Effects resulting from Equilibria between Ion Pairs Reactions between Neutral Molecules to Give two Oppositely Charged Ions Acid-Base equilibria between neutral species Equilibria for the acylation of neutral molecules Effects of Salts on Product Distribution for Reactions Taking Plac e Within Ion Pairs Reactions of "activated sulfoxides", S m -O-CO-R, X Epoxide ring opening in acid media Electrophilic additions to alkenes 229

7 Aromatic electrophilic substitutions Reductions by silanes in acid media Carbon-Carbon bond formation in oxidizing media Reactions Involving Radical Ions Photoisomerizations Photochemical organic reactions Reactivity of aromatic radical cations 23 7 References Salt Effects in Organometallic Chemistry Main Group Metals : Li, Mg Salt Effects in Organolithium Chemistry Salt effects involving the organolithium reagent Salt effects onvolving the substrate Stabilization of a-halo organolithium reagents by lithium salts : )C(X)Li (carbenoids) Case of organolithium reagents of the type R(Li)C=O Structure and reactivity of lithium amides Salt Effects in Grignard Reagent Chemistry Structure of Grignard reagents Salt effects Salt Effects in Transition Metal Chemistry Anion Effects Anion effects on the structure of complexes Effect of Xe anions on nucleophilicity of complexes Enhancement by anions of the reducing power of zerovalen t metal complexes Anion effects on the stereo- and regioselectivity of reactions catalyzed by palladium complexes Cation Effects Cation participation in migratory insertions Cation effects on the structure of anionic complexes Cation effects on the reactivity of anionic complexes Reactions Taking Place Within a Contact Ion Pair 27 9 References Appendix Revision of Some General Concepts Ionic Strength of a Solution Acidity Functions Solvent Classification Protic and Aprotic Solvents Donor and Acceptor Solvents 291

8 Donor solvents; donor number scale Acceptor solvents ; acceptor number scale Ionic Associations Coulombic Interactions "Hard" and "Soft" Ions (HSAB Classification : Hard and Soft Acids and Bases) Preferential Ionic Associations : "Symbiotic Effect" The Various Types of Ion Pair Concept of Aggregates Perturbation Theory Applied to Chemical Reactivity Klopman Equation : Charge and Orbital Control Applications to Reactivity Reaction kinetics Reaction regioselectivity Application to the HSAB Principle : Interactions Between Soft Ion s (Symbiotic Effect) Concerning Transition Metal Chemistry Degree of Coordination Unsaturation of a Transition Metal in a Complex Formal Oxidation State of a Transition Metal in a Complex Oxidative Addition and Reductive Elimination Intramolecular Insertions Hydrophobic and Hydrophilic Effects ; Salting-In and Salting-Out Effects 30 1 References Supplement - Recent Publications 30 5 Index 311

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