The α-effect and its modulation by solvent

[1]  E. A. Moelwyn-Hughes The Kinetics of Reactions in Solutions. , 1933 .

[2]  E. Hughes,et al.  55. Mechanism of substitution at a saturated carbon atom. Part IV. A discussion of constitutional and solvent effects on the mechanism, kinetics, velocity, and orientation of substitution , 1935 .

[3]  R. Bell,et al.  The Theory of Reactions Involving Proton Transfers , 1936 .

[4]  M. G. Evans,et al.  Inertia and driving force of chemical reactions , 1938 .

[5]  J E Leffler,et al.  Parameters for the Description of Transition States. , 1953, Science.

[6]  C. Gardner Swain,et al.  Quantitative Correlation of Relative Rates. Comparison of Hydroxide Ion with Other Nucleophilic Reagents toward Alkyl Halides, Esters, Epoxides and Acyl Halides1 , 1953 .

[7]  George S. Hammond,et al.  A Correlation of Reaction Rates , 1955 .

[8]  K. Wiberg,et al.  The Mechanisms of Hydrogen Peroxide Reactions. II. A Comparison of the Reactivity of Hydroxyl Ion and Hydroperoxide Ion toward Benzonitrile , 1955 .

[9]  W. Jencks The Reaction of Hydroxylamine with Activated Acyl Groups. II. Mechanism of the Reaction , 1958 .

[10]  J. Saltiel,et al.  The Reaction of Diazonium Salts with Nucleophiles. VIII. The Formation of Diazosulfones and the Application of Linear Free Energy Equations to Diazonium Salt Reactions1 , 1961 .

[11]  R. Pearson,et al.  Nucleophilic Reactivity of the Hydrogen Peroxide Anion: Distinction Between SN2 and SN1 CB Mechanisms , 1962 .

[12]  O. Exner,et al.  Acyl derivatives of hydroxylamine. XII. Dissociation constants of hydroxamic acids and their functional derivatives , 1965 .

[13]  E. Thornton A simple theory for predicting the effects of substituent changes on transition-state geometry , 1967 .

[14]  T. C. Bruice,et al.  alpha. Effect. II. Displacements on sp3 carbon , 1967 .

[15]  Rudolph A. Marcus,et al.  Theoretical relations among rate constants, barriers, and Broensted slopes of chemical reactions , 1968 .

[16]  W. Jencks,et al.  Nonlinear structure-reactivity correlations. The reactivity of nucleophilic reagents toward esters , 1968 .

[17]  R. E. Uschold,et al.  Acidity in nonaqueous solvents. VI. Further studies of weak acids in dimethyl sulfoxide solution , 1968 .

[18]  S. Ōae,et al.  The α Effect. Aminolysis on a Saturated Carbon Atom , 1969 .

[19]  W. Jencks Catalysis in chemistry and enzymology , 1969 .

[20]  Alan J. Parker,et al.  Protic-dipolar aprotic solvent effects on rates of bimolecular reactions , 1969 .

[21]  F. Rallo,et al.  Calorimetric determination of partial molar enthalpies of solution of water and dimethylsulfoxide in their mixtures , 1970 .

[22]  R. F. Hudson,et al.  Enhanced reactivity of nucleophiles: orbital symmetry and the so-called “α-effect” , 1970 .

[23]  R. F. Hudson,et al.  Enhanced reactivity of nucleophiles: the “α-effect” in reactions of benzyl bromide , 1970 .

[24]  Y. Ashani,et al.  Nucleophilicity of some reactivators of phosphorylated acetylcholinesterase. , 1971, Journal of medicinal chemistry.

[25]  J. Dixon,et al.  alpha. Effect. IV. Additional observation on the .alpha. effect employing malachite green as substrate , 1971 .

[26]  E. A. Symons Hydrogen Gas Solubility in the Dimethyl Sulfoxide – Water System: A Further Clue to Solvent Structure in These Media , 1971 .

[27]  E. Behrman,et al.  Nucleophilic reactivity of peroxy anions , 1972 .

[28]  J. Dixon,et al.  alpha. Effect. V. Kinetic and thermodynamic nature of the .alpha. effect for amine nucleophiles , 1972 .

[29]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[30]  L. Deady,et al.  Search for the .alpha. effect among heteroaromatic nitrogen nucleophiles , 1972 .

[31]  Calvin D. Ritchie,et al.  Nucleophilic reactivities toward cations , 1972 .

[32]  J. F. Liebman,et al.  Aromatic transition states and the .alpha. effect , 1973 .

[33]  John O. Edwards,et al.  The alpha effect. A review , 1973 .

[34]  M. P. Eastman,et al.  Ultrasound propagation in binary mixtures of dimethyl sulfoxide and water , 1974 .

[35]  R. Benoit,et al.  Some Thermodynamic Properties of the Dimethylsulfoxide–Water and Propylene Carbonate–Water Systems at 25 °C , 1974 .

[36]  C. D. Johnson Linear free energy relations and the reactivity-selectivity principle , 1975 .

[37]  Janos H. Fendler,et al.  Catalysis in micellar and macromolecular systems , 1975 .

[38]  F. Furia,et al.  The Influence of solvent and crown polyethers on the nucleophilic reactivity of potassium tert‐Butylperoxide, potassium tert‐Butoxide, and some other oxygen bases , 1975 .

[39]  G. Douhéret,et al.  Thermodynamic and physical behaviour of water + acetonitrile mixtures. Dielectric properties , 1976 .

[40]  D. Macdonald,et al.  Thermal pressure and energy–volume coefficients for the acetonitrile + water system , 1976 .

[41]  M. Chemla,et al.  Solvation of tetrabutylammonium bromide in water + acetonitrile mixtures at 298.15 K from vapour pressure measurements of dilute solutions , 1976 .

[42]  I. Kolthoff,et al.  Comparison of substituent effects on dissociation and conjugation of phenols with those of carboxylic acids in acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide , 1976 .

[43]  Thomas H. Lowry,et al.  Mechanism and Theory in Organic Chemistry , 1976 .

[44]  D. Hupe,et al.  The effect of solvation on Broensted .beta. values for proton transfer reactions , 1977 .

[45]  W. Jencks,et al.  Nonlinear structure-reactivity correlations. Acyl transfer between sulfur and oxygen nucleophiles , 1977 .

[46]  E. Buncel,et al.  Physical Organic Chemistry of Reactions in Dimethyl Sulphoxide , 1977 .

[47]  A. Pross The Reactivity—Selectivity Principle and its Mechanistic Applications , 1977 .

[48]  Charles Tanford,et al.  The Hydrophobic Effect: Formation of Micelles and Biological Membranes , 1991 .

[49]  V. Veselov,et al.  The α-Effect in the Chemistry of Organic Compounds , 1978 .

[50]  E. Buncel,et al.  Initial-state and transition-state solvent effects on reaction rates and the use of thermodynamic transfer functions , 1979 .

[51]  C. A. Bunton,et al.  Hydrophobic and coulombic interactions in the micellar binding of phenols and phenoxide ions , 1979 .

[52]  C. Chuaqui,et al.  Bond scission in sulfur compounds. 13. Reactivity-selectivity correlations. 3. The .alpha. effect at saturated carbon. Reactivity studies of methyl phenyl sulfates with nucleophiles , 1980 .

[53]  C. A. Bunton,et al.  Reactions in micelles of cetyltrimethylammonium hydroxide. Test of the pseudophase model for kinetics , 1982 .

[54]  C. Chuaqui,et al.  Reactivity-selectivity correlations. 4. The .alpha. effect in SN2 reactions at sp3 carbon. The reactions of hydrogen peroxide anion with methyl phenyl sulfates , 1982 .

[55]  H. Schlegel,et al.  Theoretical studies of SN2 transition states, the alpha effect , 1982 .

[56]  A. L. Crumbliss,et al.  Temperature-dependent acid dissociation constants (K/sub a/,. delta. H/sub a/,. delta. S/sub a/) for a series of nitrogen-substituted hydroxamic acids in aqueous solution , 1982 .

[57]  S. Hoz The .alpha. effect: on the origin of transition-state stabilization , 1982 .

[58]  H. Inoue,et al.  Mechanism for the Oxidative Cleavage of Electron-deficient Acetylenes with Alkaline Hydrogen Peroxide , 1983 .

[59]  E. W. Della,et al.  Absence of an .alpha.-effect in the gas-phase nucleophilic reactions of hydroperoxide ion , 1983 .

[60]  E. Buncel,et al.  Can ground-state destabilization of an α-nucleophile induce an α-effect? , 1983 .

[61]  P. Gosselin,et al.  Enhanced reactivity of an α-nucleophile in water-dimethyl sulfoxide mixtures. A transition state effect. , 1984 .

[62]  E. Buncel,et al.  Pitfalls in the determination of the α-effect by a two-point analysis. The effect of solvent on the α-effect. , 1984 .

[63]  W. Jencks,et al.  Nucleophilic reactivity toward acetyl chloride in water , 1984 .

[64]  E. B. Troughton,et al.  Ion pairing and reactivity of enolate anions. 6. Kinetics and thermodynamics for reaction of alkali acetylacetonates with alkyl halides in dimethyl sulfoxide , 1985 .

[65]  William P. Jencks,et al.  A primer for the Bema Hapothle. An empirical approach to the characterization of changing transition-state structures , 1985 .

[66]  Shmaryahu Hoz,et al.  The α-Effect: A Critical Examination of the Phenomenon and Its Origin , 1985 .

[67]  Ross Stewart,et al.  The proton, applications to organic chemistry , 1985 .

[68]  S. Ōae,et al.  Importance of repulsion of lone electron pairs in the enhanced reactivity of 1,8-naphthyridine and the large α-effect of hydrazine in the aminolyses of p-toluenesulfonyl chloride , 1986 .

[69]  C. Ritchie Cation–anion combination reactions. 26. A review , 1986 .

[70]  C. J. Murray,et al.  Nucleophilic addition to olefins. 18. Kinetics of the addition of primary amines and .alpha.-effect nucleophiles to benzylidene Meldrum's acid , 1986 .

[71]  F. Bordwell,et al.  Rate-equilibrium relationships for reactions of families of carbanion nucleophiles with N-benzyl-N,N-dimethylanilinium cations and with alkyl chlorides, bromides, and iodides , 1986 .

[72]  K. Miyaji,et al.  Solvation of Anions in Water–Acetonitrile Mixtures , 1986 .

[73]  J. Edwards,et al.  Reaction rates for nucleophiles with cyanogen chloride: Comparison with two other digonal carbon compounds , 1986 .

[74]  E. Buncel,et al.  The solvent effect on the α-effect , 1986 .

[75]  R. Moss,et al.  α-Effect of an organoiodinane oxyanion nucleophile: absence of an unusual solvent effect , 1987 .

[76]  Erwin Buncel,et al.  The reactivity selectivity principle: Should it ever be used? , 1987 .

[77]  C. F. Bernasconi Intrinsic barriers of reactions and the principle of nonperfect synchronization , 1987 .

[78]  M. Symons,et al.  Solvation of cyanoalkanes [CH3CN and (CH3)3CCN]. An infrared and nuclear magnetic resonance study , 1988 .

[79]  C. Reichardt Solvents and Solvent Effects in Organic Chemistry , 1988 .

[80]  C. A. Bunton,et al.  Nucleophilic reactions in zwitterionic micelles of amine oxide or betaine sulfonate surfactants , 1989 .

[81]  D. Kwon,et al.  The Effect of Medium of the $\alpha$ -Effect , 1989 .

[82]  E. Buncel,et al.  Solvent-independent transition-state structure for acyl-transfer reactions. A novel strategy for construction of a Broensted correlation , 1989 .

[83]  Y. Whang,et al.  Acidities of carboxamides, hydroxamic acids, carbohydrazides, benzenesulfonamides, and benzenesulfonohydrazides in DMSO solution , 1990 .

[84]  D. Herschlag,et al.  Nucleophiles of high reactivity in phosphoryl transfer reactions: .alpha.-effect compounds and fluoride ion , 1990 .

[85]  I. Um,et al.  Absence of Polarizability Effect on the ${\alpha}$-Effect in Aminolyses of p-Nitrophenyl Acetate and S-p-Nitrophenyl Thioacetate , 1990 .

[86]  J. Gal,et al.  The gas-phase acidity and the acidic site of acetohydroxamic acid: a FT-ICR study , 1990 .

[87]  I. Um,et al.  Reaction Mechanism for Acyl-Transfer Reactions of Aryl Acetates with Aryloxides , 1990 .

[88]  I. Um The Effect of Medium on the ${\alphat}$-Effect (Part 2) , 1990 .

[89]  C. Lion,et al.  Non-linear Brønsted correlations: evidence for a levelling off in the reactivity of oximate ions in aqueous solution , 1991 .

[90]  C. F. Bernasconi,et al.  Kinetics of amine addition to benzylidenemalonodialdehyde in 50% dimethyl sulfoxide - 50% water , 1991 .

[91]  F. Quina,et al.  Ion Binding and Reactivity at Charged Aqueous Interfaces , 1991 .

[92]  J. Salmon,et al.  Reactivity patterns of N-methylbenzhydroxamates. I. Studies of methyl transfer between N-methylbenzhydroxamates and arenesulfonates , 1991 .

[93]  J. Gandler,et al.  Nucleophilic reactivity: nucleophilic aromatic substitution reactions of 2,4-dinitrochlorobenzene and picryl chloride in aqueous and methanol solutions , 1992 .

[94]  C. F. Bernasconi The Principle of Non-perfect Synchronization , 1992 .

[95]  Seung-Eun Lee,et al.  Disappearance of the ${\alpha}$-Effect : Reaction of p-Nitrophenyl Acetate with Various Aryloxides and Benzohydroxamates in the Presence of Cetyltrimethylammonium Bromide , 1992 .

[96]  Um Ik-Hwan The Effect of Solvation and Polarizability on the $\alpha$ -Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Benzoate with Various Anionic Nucleophiles , 1992 .

[97]  M. Berkowitz,et al.  Local structural order and molecular associations in water-DMSO mixtures. Molecular dynamics study , 1992 .

[98]  I. Um,et al.  Solvent effect on rate for anionic nucleophilic substitution reaction of 4-nitrophenyl acetate in aqueous acetonitrile , 1992 .

[99]  Um Ik-Hwan,et al.  The Effect of Solvent on the $\alpha$-Effect(3): Nucleophilic Substitution Reactions of Aryl Acetates in $MeCN-H_2O$ Mixtures of Varying Compositions , 1992 .

[100]  D. Kwon,et al.  Solvent Effect on the α-Effect in Nucleophilic Substitution Reaction of 4-Nitrophenyl Acetate in MeCN-$H_{2}O$ Mixtures , 1993 .

[101]  L. García‐Río,et al.  Reactivity of nucleophilic nitrogen compounds towards the nitroso group , 1993 .

[102]  Debbie C. Mulhearn,et al.  α-effect in Menschutkin alkylations , 1993 .

[103]  O. Exner,et al.  Dissociation of Hydroxamic Acids: Solvent Effects , 1993 .

[104]  J. W. Bunting,et al.  Nucleophilicity towards a vinylic carbon atom: rate constants for the addition of amines to the 1-methyl-4-vinylpyridinium cation in aqueous solution , 1994 .

[105]  I. Um,et al.  The Effects of Solvation and Polarizability on the Reaction of S-p-Nitrophenyl Thiobenzoate with Various Anionic Nucleophiles , 1994 .

[106]  A. Bagno,et al.  Site of Ionization of Hydroxamic Acids Probed by Heteronuclear NMR Relaxation Rate and NOE Measurements. An Experimental and Theoretical Study , 1994 .

[107]  O. E. Seoud,et al.  Kinetics and mechanism of the hydrolysis of substituted phenyl benzoates catalyzed by the o‐iodosobenzoate anion , 1995 .

[108]  Erwin Buncel,et al.  Origin of the Bell-Shaped .alpha.-Effect-Solvent Composition Plots. pKa-Solvent Dependence of the .alpha.-Effect at a Phosphorus Center , 1995 .

[109]  C. F. Bernasconi,et al.  KINETICS OF THE REACTIONS OF BETA -METHOXY-ALPHA -NITROSILBENE WITH METHOXYAMINE AND N-METHYLMETHOXYAMINE. DIRECT OBSERVATION OF THE INTERMEDIATE IN N UCLEOPHILIC VINYLIC SUBSTITUTION , 1995 .

[110]  I. Um,et al.  The effect of solvent on the α-effect: Abnormal nucleophilic reactivity of substituted acetophenone oximate anions in aqueous DMSO , 1995 .

[111]  K. Patel,et al.  O-Alkylation of N-Phenylhydroxylamine in Dimethyl Sulfoxide with Methylarenesulfonates , 1996 .

[112]  J. Toullec,et al.  Cetyltrimethylammonium hydroperoxide: an efficient reagent for promoting phosphate ester hydrolysis , 1996 .

[113]  I. Um,et al.  Effect of Solvent on the α-Effect: Nucleophilic Substitution Reactions of p-Nitrophenyl Acetate with m-Chlorophenoxide and Benzohydroxamates in MeCN−H2O Mixtures of Varying Compositions , 1997 .

[114]  G. Moutiers,et al.  Similar catalytic behaviour of oximate and phenoxide bases in theionization of bis(2,4-dinitrophenyl)methane in 50% water– 50%Me2SO. Revisiting the role of solvational imbalances indetermining the nucleophilic reactivity of α-effect oximate bases , 1997 .

[115]  I. Um,et al.  The Effect of Acyl Substituent on the α-Effect in the Aminolysis of p-Nitrophenyl X-Substituted Benzoates , 1997 .

[116]  K. Patel,et al.  Evidence That the α-Effects in Methyl Transfers from Aryldimethylsulfonium Salts Correlate with Single-Electron-Transfer Characteristics , 1997 .

[117]  S. Ōae,et al.  LACK OF ENHANCed REACTIVITY OF α-NUCLEOPHILES In THE SN2 REACTIONS OF BENZYL BROMIDES AND SMALL α-EFFECT In THE MICHAEL ADDITION RECTION OF AMIDES TO P-TOLYL VINYL SULFONE , 1997 .

[118]  K. Patel,et al.  alpha-Effect with Substituted N-Methylbenzohydroxamates and Substituted Phenyldimethylsulfonium Salts: Toward Understanding of an Intrinsic alpha-Effect. , 1997, The Journal of organic chemistry.

[119]  I. Um,et al.  An unusual ground-state stabilization effect and origins of the alpha-effect in aminolyses of Y-substituted phenyl X-substituted benzoates , 1998 .

[120]  M. Wong,et al.  Alpha-effect nucleophiles and azide ion: effective charge studies of displacement reactions at esters , 1998 .

[121]  P. R. Norman,et al.  Kinetic and mechanistic studies of the reaction of a range of bases and metal-hydroxo complexes with the phosphonate ester 2,4-dinitrophenyl ethyl methylphosphonate in aqueous solution , 1998 .

[122]  I. Um,et al.  An Unexpectedly Small α-Effect in Nucleophilic Attack at sp-Hybridized Carbon: Michael-Type Additions of Primary Amines to 3-Butyn-2-one , 1998 .

[123]  K. R. Fountain,et al.  The alpha-Effect in Benzyl Transfers from Benzylphenylmethyl Sulfonium Salts to N-Methylbenzohydroxamate Anions. , 1999, The Journal of organic chemistry.

[124]  G. Moutiers,et al.  Rapid Marcus Curvature Due to Extremely Strong Solvational Imbalances inthe Deprotonation of a Trinitrobenzylic Carbon Acid by Oximate Bases , 1999 .

[125]  E. Castro Kinetics and Mechanisms of Reactions of Thiol, Thiono, and Dithio Analogues of Carboxylic Esters with Nucleophiles. , 1999, Chemical reviews.

[126]  Um,et al.  The origin of the alpha-effect: dissection of ground-state and transition-state contributions , 2000, The Journal of organic chemistry.

[127]  Ikran Eum,et al.  The origin of the alpha-effect: Reactions of p-nitrophenyl X-substituted benzenesulfonates with butane-2,3-dione monoximate and p-chlorophenoxide , 2000 .

[128]  F. Mancin,et al.  Activation of oximic nucleophiles by coordination of transition metal ions , 2000 .

[129]  Young-Min Park,et al.  The effect of solvent on the α-effect: the MeCN–H2O solvent system , 2000 .

[130]  J. Richard,et al.  Structure-Reactivity Relationships and Intrinsic Reaction Barriers for Nucleophile Additions to a Quinone Methide: A Strongly Resonance-Stabilized Carbocation , 2000 .

[131]  Min,et al.  Effect of acyl substituents on the reaction mechanism for aminolyses of 4-nitrophenyl X-substituted benzoates , 2000, The Journal of organic chemistry.

[132]  Myungjo J. Kim,et al.  First definitive spectroscopic evidence for a stable intermediate in a sulfinyl-transfer reaction: reaction of dibenzo[1,2]oxathiin-6-oxide with sodium ethoxide in anhydrous ethanol , 2000 .

[133]  R. Moss,et al.  Kinetics of Cleavage of Paraoxon and Parathion by Cetyltrimethylammonium Iodosobenzoate , 2001 .

[134]  E. Buncel,et al.  Solvent effect on the alpha-effect for the reactions of aryl acetates with butane-2,3-dione monoximate and p-chlorophenoxide in MeCN-H2O mixtures. , 2001, The Journal of organic chemistry.

[135]  Jin Hong,et al.  The effect of solvent on the α-effect: CO, PO and SO2 centers , 2001 .

[136]  J. Toullec,et al.  Catalysis of Phosphate Triester Hydrolysis by Micelles of Hexadecyltrimethylammonium anti-Pyruvaldehyde 1-Oximate , 2001 .

[137]  G. Vanloon,et al.  Mechanisms of abiotic degradation and soil–water interactions of pesticides and other hydrophobic organic compounds. Part 3. Nucleophilic displacement at the phosphorus centre of the pesticide fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl) phosphorothioate] by oxygen nucleophiles in aqueous s , 2001 .

[138]  G. Moutiers,et al.  The α-Effect in SNAr Substitutions − Reaction between Oximate Nucleophiles and 2,4-Dinitrofluorobenzene in Aqueous Solution , 2001 .

[139]  E. Buncel,et al.  Ground-State versus Transition-State Effects on the α-Effect as Expressed by Solvent Effects , 2001 .

[140]  I. Um,et al.  The effect of acyl substituents on the α-effect: contrasting α-effect profiles for reactions of 4-nitrophenyl substituted benzoates with neutral and anionic nucleophiles , 2001 .

[141]  Seung-Eun Lee,et al.  The Effect of Medium on the α-Effect: Nucleophilic Substitution Reaction of p-Nitrophenyl Diphenyl Phosphinate with Butane-2,3-dione Monoximate and Substituted Phenoxides in Cationic Micelles † , 2002 .

[142]  R. Moss,et al.  Phosphorolytic reactivity of o-iodosylcarboxylates and related nucleophiles. , 2002, Chemical reviews.

[143]  E. Buncel,et al.  Reactions of oximate alpha-nucleophiles with esters: evidence from solvation effects for substantial decoupling of desolvation and bond formation. , 2002, Journal of the American Chemical Society.

[144]  G. Moutiers,et al.  The levelling effect of solvational imbalances in the reactions of oximate alpha-nucleophiles with electrophilic phosphorus centers. Relevance to detoxification of organophosphorus esters. , 2003, Chemical communications.

[145]  J. Driskell,et al.  The alpha-effect in methyl transfers from S-methyldibenzothiophenium fluoroborate to substituted N-methylbenzohydroxamates. , 2003, The Journal of organic chemistry.