RECENT DEVELOPMENT IN THE STUDY OF SN2 REACTIONS AT HETEROATOMS AND ION PAIR SYSTEMS

Present review outlines the experimental and theoretical studies on the SN2 reactions at heteroatoms (N, O and S) and ion pair systems in recent years, especially introduce research carried out at our group in detail. The similarities and differences between SN2 at heteroatoms and at carbon are discussed. Some new structure–energy relationships were proposed. The accuracy of various theoretical schemes for calculating potential energy surfaces has been assessed.

[1]  Stanley G. Smith,et al.  Alleged SN2 finkelstein substitutions of t-butyl bromide , 1959 .

[2]  Rudolph A. Marcus,et al.  Chemical and Electrochemical Electron-Transfer Theory , 1964 .

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

[4]  J. L. Kice,et al.  The relative nucleophilicity of some common nucleophiles toward sulfenyl sulfur. The nucleophile- and acid-catalyzed racemization of optically active phenyl benzenethiosulfinate , 1968 .

[5]  E. Ciuffarin,et al.  Formation of an intermediate in nucleophilic substitution at dicoordinated sulfur , 1970 .

[6]  E. Ciuffarin,et al.  Nucleophilic substitution at dicoordinated sulfur. Effect of the leaving group on the reaction between triphenylmethyl sulfenyl derivatives and butylamine , 1970 .

[7]  E. P. Kyba.  Nucleophilic substitution at phosphorus in tertiary phosphines. Inversion of configuration , 1975 .

[8]  T. E. Rogers,et al.  Catalysis of the reaction of morpholine with phenyl benzenethiolsulfonate by halide ions and thiocyanate. Possible evidence for an intermediate on the reaction coordinate in a substitution at sulfenyl sulfur , 1976 .

[9]  E. P. Kyba.  Nucleophilic substitution at phosphorus in tertiary phosphines. Evidence against pseudorotation in a potential intermediate , 1976 .

[10]  J. L. Kice,et al.  Reactivity of nucleophiles toward and the site of nucleophilic attack on phenyl benzenethiolsulfinate , 1979 .

[11]  H. Schlegel,et al.  Theoretical studies of SN2 transition states. 2. Intrinsic barriers, rate-equilibrium relationships, and the Marcus equation , 1981 .

[12]  P. Siegbahn,et al.  The reactions between negative hydrogen ions and silane , 1984 .

[13]  M. Gordon,et al.  A Theoretical Study of Fluorine Atom and Fluoride Ion Attack on Methane and Silane , 1985 .

[14]  Peter J. Smith,et al.  Large concentration effects on the magnitude of secondary alpha-deuterium kinetic isotope effects , 1985 .

[15]  P. Beak,et al.  Geometry of formal nucleophilic substitution at first-row heteroatoms: the transfer of oxygen from nitrogen to phosphorus , 1986 .

[16]  R. R. Holmes,et al.  Pathways for nucleophilic substitution at silicon. A molecular orbital approach , 1987 .

[17]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[18]  K. Westaway,et al.  Isotope effects in nucleophilic substitution reactions. VI: The effect of ion pairing on the transition state structure of SN2 reactions , 1988 .

[19]  K. Westaway,et al.  Isotope effects in nucleophilic substitution reactions. VII. The effect of ion pairing on the substituent effects on SN2 transition state structure , 1989 .

[20]  Z. Lai,et al.  Solvent effects on SN2 transition state structure. II: The effect of ion pairing on the solvent effect on transition state structure , 1989 .

[21]  M. Famulok,et al.  Synthesis of O‐Acetyl‐N (4‐biphenylyl)hydroxylamine (“NAcetoxy‐4‐aminobiphenyl”), an Ultimate Metabolite of Carcinogenic 4‐Aminobiphenyl, and Its Reaction with Deoxyguanosine , 1989 .

[22]  Ender Erdik,et al.  Electrophilic amination of carbanions , 1989 .

[23]  Rainer Glaser,et al.  Charge Transfers and Polarizations in Bonds to Silicon. Organosilanes and the S N 2(Si) Reaction of SiH 4 + F - . An Ab Initio Study , 1989 .

[24]  M. Novak,et al.  SN2 reactions of a carbon nucleophile with N-aryl-O-pivaloylhydroxylamines: a model for in vivo reactions of carcinogenic metabolites of aromatic amines , 1989 .

[25]  S. Bachrach.  Nucleophilic substitution at oxygen: the reaction of phosphine and ammonia with ammonia oxide. An ab initio investigation , 1990 .

[26]  Michael Famulok,et al.  SN2 at nitrogen : the reaction of N-(4-cyanophenyl)-O-diphenylphosphinoylhydroxylamine with N-methylaniline. A model for the reactions of ultimate carcinogens of aromatic amines with (bio)nucleophiles , 1990 .

[27]  R. R. Holmes.  The stereochemistry of nucleophilic substitution of tetracoordinate silicon , 1990 .

[28]  Michael Novak,et al.  Mechanism of the reaction of carbon and nitrogen nucleophiles with the model carcinogens O-pivaloyl-N-arylhydroxylamines: competing SN2 substitution and SN1 solvolysis , 1991 .

[29]  P. Beak,et al.  The endocyclic restriction test: experimental evaluation of transition-structure geometry for a nucleophilic displacement at neutral nitrogen , 1991 .

[30]  A. Becke.  Density-functional thermochemistry. II: The effect of the Perdew-Wang generalized-gradient correlation correction , 1992 .

[31]  Axel D. Becke,et al.  Density-functional thermochemistry. I. The effect of the exchange-only gradient correction , 1992 .

[32]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[33]  Debbie C. Mulhearn,et al.  Theoretical studies of nucleophilic substitution at phosphorus. Phosphine + hydride .fwdarw. H- + PH3 , 1993 .

[34]  Henry F. Schaefer,et al.  SN2 reaction at neutral nitrogen: transition state geometries and intrinsic barriers. , 1993 .

[35]  Jacopo Tomasi,et al.  Molecular Interactions in Solution: An Overview of Methods Based on Continuous Distributions of the Solvent , 1994 .

[36]  David J. Wales,et al.  Gradient Line Reaction Path for an SN2 Reaction at Neutral Nitrogen , 1994 .

[37]  ab Mikhail N. Glukhovtsev,et al.  Gas-Phase Non-Identity SN2 Reactions of Halide Anions with Methyl Halides: A High-Level Computational Study , 1995 .

[38]  Paul von Ragué Schleyer,et al.  Ion Pair SN2 Reactions. Theoretical Study of Inversion and Retention Mechanisms , 1995 .

[39]  Alexander M. Mebel,et al.  MODIFICATION OF THE GAUSSIAN-2 THEORETICAL MODEL : THE USE OF COUPLED-CLUSTER ENERGIES, DENSITY-FUNCTIONAL GEOMETRIES, AND FREQUENCIES , 1995 .

[40]  Mikhail N. Glukhovtsev,et al.  Gas-Phase Identity SN2 Reactions of Halide Ions at Neutral Nitrogen: A High-Level Computational Study , 1995 .

[41]  Tuvia Sheradsky,et al.  Intramolecular nucleophilic substitution on nitrogen. a new heterocyclic synthesis , 1995 .

[42]  Junqi Li,et al.  The Endocyclic Restriction Test: Investigation of the Geometries of Nucleophilic Substitution at Phosphorus(III) and Phosphorus(V) , 1996 .

[43]  ab Mikhail N. Glukhovtsev,et al.  Gas-Phase Identity SN2 Reactions of Halide Anions and Methyl Halides with Retention of Configuration , 1996 .

[44]  Steven M. Bachrach,et al.  Nucleophilic Substitution at Sulfur: S N 2 or Addition-Elimination? , 1996 .

[45]  Debbie C. Mulhearn,et al.  Selective Nucleophilic Attack of Trisulfides. An ab Initio Study , 1996 .

[46]  L. Radom,et al.  The performance of B3-LYP density functional theory in describing SN2 reactions at saturated carbon , 1996 .

[47]  Andrew Streitwieser,et al.  Theoretical Study of Ion Pair SN2 Reactions: Ethyl vs Methyl Reactivities and Extension to Higher Alkyls , 1997 .

[48]  V. Barone,et al.  Solvent effects on an SN2 reaction profile , 1998 .

[49]  Andrew Streitwieser,et al.  Theoretical study of structure of alkali metal cyanates and isocyanates and their related ion pair SN2 reactions , 1998 .

[50]  Vincenzo Barone,et al.  Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models , 1998 .

[51]  H. Basch,et al.  INTRINSIC BARRIERS IN IDENTITY SN2 REACTIONS AND THE PERIODIC TABLE , 1999 .

[52]  Donald G. Truhlar,et al.  Adiabatic connection for kinetics , 2000 .

[53]  V. Bierbaum,et al.  Gas phase reactions of NH2Cl with anionic nucleophiles: Nucleophilic substitution at neutral nitrogen , 2001, Journal of the American Society for Mass Spectrometry.

[54]  Bernd Ensing,et al.  Solvation Effects on the SN2 Reaction between CH3Cl and Cl- in Water , 2001 .

[55]  T. Sølling,et al.  A high-level ab initio investigation of identity and nonidentity gas-phase SN2 reactions of halide ions with halophosphines , 2001 .

[56]  S. Bachrach,et al.  Theoretical study of nucleophilic substitution at two-coordinate sulfur. , 2001, The Journal of organic chemistry.

[57]  Yi Ren,et al.  A G2(+) level investigation of the gas-phase identity nucleophilic substitution at neutral oxygen , 2002 .

[58]  Harold Basch,et al.  The periodic table and the intrinsic barrier in s(n)2 reactions. , 2002, The Journal of organic chemistry.

[59]  Yi Ren,et al.  The performance of density function theory in describing gas-phase SN2 reactions at saturated nitrogen , 2002 .

[60]  Debbie C. Mulhearn,et al.  Effect of ring strain on the thiolate-disulfide exchange. A computational study. , 2002, The Journal of organic chemistry.

[61]  T. E. Rogers,et al.  Relative nucleophilicity of common nucleophiles toward sulfinyl sulfur. Comparison of the relative reactivity of different nucleophiles toward sulfinyl vs. sulfonyl sulfur , 2002 .

[62]  Jon K. Laerdahl,et al.  Gas phase nucleophilic substitution , 2002 .

[63]  Yi Ren,et al.  Hybrid DFT study on the gas-phase SN2 reactions at neutral oxygen , 2003 .

[64]  S. Bachrach,et al.  Theoretical study of nucleophilic substitution at the disulfide bridge of cyclo-l-cystine. , 2003, The Journal of organic chemistry.

[65]  Yi Ren,et al.  A comprehensive theoretical study on the identity ion pair SN2 reactions of LiX with NH2X (X=F, Cl, Br and I), structure, mechanism and potential energy surface , 2003 .

[66]  S. Bachrach,et al.  Effect of Micro and Bulk Solvation on the Mechanism of Nucleophilic Substitution at Sulfur in Disulfides , 2003 .

[67]  Yi Ren,et al.  Modified Gaussian‐2 level investigation of the identity ion‐pair SN2 reactions of lithium halide and methyl halide with inversion and retention mechanisms , 2004, J. Comput. Chem..

[68]  S. Bachrach,et al.  Nucleophilic attack at selenium in diselenides and selenosulfides. A computational study , 2004 .

[69]  Yi Ren,et al.  A G2(+) level investigation of the gas-phase non-identity SN2 reactions of halides with halodimethylamine , 2004, Journal of the American Society for Mass Spectrometry.

[70]  Jie Ren,et al.  A theoretical study of the ion pair SN2 reaction between lithium isocyanates with methyl fluoride with inversion and retention mechanism , 2004 .

[71]  Yi Ren,et al.  Ion Pair SN2 Reactions at Nitrogen: A High-Level G2M(+) Computational Study , 2004 .

[72]  S. Bachrach,et al.  Theoretical study of nucleophilic substitution at sulfur in sulfinyl derivatives. , 2005, The Journal of organic chemistry.

[73]  Jie Ren,et al.  Theoretical investigation of ion pair SN2 reactions of alkali isothiocyanates with alkyl halides. Part 1. Reaction of lithium isothiocyanate and methyl fluoride with inversion mechanism , 2005 .