The Anomeric Effect and Associated Stereoelectronic Effects

Downloaded by 80.82.77.83 on May 29, 2018 | https://pubs.acs.org Publication Date: November 23, 1993 | doi: 10.1021/bk-1993-0539.ix002

Author Index Anderson, Gary, 227 Andrews, C. Webster, 114 Bowen, J. Phillip, 114 Cameron, Dale R., 256 DeShong, Philip, 227 Deslongchamps, P., 26 Edward, John T., 1 Fraser-Reid, Bert, 114 Grein, F., 205 Jalluri, Ravi K., 277 Kirby, Anthony J., 55 Laidig, Κ. E., 176 Le, Thuy X., 227 Lerner, Laura E., 156 Lessen, Thomas Α., 227 Leung, Ronald Y. N., 126 Lim, Carmay, 240

Ma, J., 176 Perrin, Charles L., 70 Petillo, Peter Α., 156 Pinto, B. Mario, 126 Sidler, D. Rick, 227 Sinnott, Michael L., 97 Slough, Greg Α., 227 Taylor, E. Will, 277 Thatcher, Gregory R. J., 6,256 Tole, Philip, 240 Vohler, Markus, 227 von Philipsborn, Wolfgang, 227 Wérstiuk, Ν. H., 176 Williams, Nicholas H., 55 Yuh, Young H., 277 Zerbe, Oliver, 227

Affiliation Index Burroughs Wellcome, 114 Duke University, 114 McGill University, 1 McMaster University, 176 Pennsylvania State University, 227 Queen's University, 6,256 Simon Fraser University, 126 Université de Sherbrooke, 26 University Chemical Laboratory, 55

University of California—San Diego, 70 University of Georgia, 114,277 University of Illinois at Chicago, 97 University of Maryland, 227 University of New Brunswick, 205 University of Toronto, 240 University of Wisconsin—Madison, 156 University of Zurich, 227

Subject Index A

Acetal hydrolysis mechanism—Continued 1,7-dioxaspiro[5.5]undecane formation, 31-33 importance, 30 kinetic cyclization of hydroxyenol ether, 35-38 mild acid cyclization of bicyclic hydroxypropyl acetal, 38-41 principle of least motion, 41-43 solvent effect, 38r

Acetal(s) anomeric and reverse anomeric effect, 205-225 biomolecularity of reactions, 101-105 Acetal hydrolysis mechanism antiperiplanar lone pair hypothesis, 16 antiperiplanar vs. synperiplanar hypothesis, 41

297 Thatcher; The Anomeric Effect and Associated Stereoelectronic Effects ACS Symposium Series; American Chemical Society: Washington, DC, 1993.


298

T H E ANOMERIC EFFECT AND ASSOCIATED STEREOELECTRONIC EFFECTS

Acetal hydrolysis mechanism—Continued transition states, 34-41 Acetal oxygen basicity, antiperiplanar lone pair hypothesis, 16 N-Acetylneuraminic acid glycosides, transition-state geometry of nonenzymic reactions, 108-109 Alkylmanganese pentacarbonyl complexes, synthesis of carbonyl derivatives, 227-228 2-Alkylthio derivatives of 1,1-dimethoxyethane, conformational analysis, 132-133 Amidine hydrolysis, antiperiplanar lone pair hypothesis, 16-17 Anomeric and gauche effect interplay in substituted 1,4-diheterocyclohexanes additivity of orbital interactions, 149,151-152 equilibrium data, 144i,148 orbital interaction component, 145ί,148-150ί Anomeric destabilization, description, 8 Anomeric effect bonding η -» σ* interactions, 55-57 carbohydrates, 277 description and definition, 6-7,70-71 electrostatic effects, 55-57 geometries and reactivities, changes, 176-177 nucleosides, 277-278 OAc groups, 59-61 origin, 79-84,156-169 postulation, 1-4 quantitative modeling, 169-173 structure and conformation, 7-14 theoretical studies, 205-206 transition-state structure and reactivity, 14-19 Anomeric effect in acetals energy analysis neutral systems, 206-213 protonated systems, 214-219 energy parameters, 223-225 nature, 222-223 π-bonding model NH systems, 22h,222 OH systems, 219-221 studies, 205-206 Anomeric effect in dimethoxymethane, application of quantum theory of atoms in molecules, 176-204 2

Anomeric groups, OAr effects, 57-59 Anomeric stabilization, definition, 8 Antiperiplanar, description, 278 Antiperiplanar lone pair hypothesis acetal hydrolysis mechanism, 16 acetal oxygen basicity, 16 amidine hydrolysis, 16-17 concept, 14-15 orthoester hydrolysis, 17-18 principle of least nuclear motion in acetals, comparison, 15 questions, 19 synperiplanar lone pair hypothesis, comparison, 16,18 stereoelectronic control in phosphoryl transfer, 19-22 See also Stereoelectronic control Apical ligands, definition, 258 Atom electron populations, dimethoxy methane conformers, 180,1811 Attractive gauche effect, definition, 127

Β Barton, anomeric effect postulation, 1,3-4 Bicyclic hydroxypropyl acetal, acid cyclization, 38-41 Biomolecularity of reactions of acetals and glycosides, evidence, 101-105 Bond critical point properties, dimethoxy methane conformers, 181 -184 bonding η -» σ* interactions anomeric effect, 57-61 description, 55-57 gauche effect, 63-68 reverse anomeric effect, 61-63 C Computational methods for O-C-N anomeric effect studies in nucleosides, 284-285 Conformation of anomeric and stereoelectronic effects computational studies, 12-13 definition and clarification, 7-9 experimental evidence, 9-10 lone pairs of electrons, 11-12 second and third row effects, 13-14 theoretical rationale, 10-11

Thatcher; The Anomeric Effect and Associated Stereoelectronic Effects ACS Symposium Series; American Chemical Society: Washington, DC, 1993.

INDEX

299

Conformational behavior, studies, 126-127 Conformational^ restrained pyranosides, hydrolysis, 116,117/ Corey, role in anomeric effect postulation, 2 Cyclic amidine hydrolysis, test of stereo electronic control, 85-90 Cyclic orthoester hydrolysis, 47-53


D 1,2-Dihetero-substituted ethanes, gauche conformations, 127-128 Dimethoxymethane, protonated, See Protonated dimethoxymethane Dimethoxymethane conformers atom electron populations, 180,181* atom energies, 180—182i bond critical point properties, 181-184 component energies, 179,180* geometric bond lengths, 179 1,8-Dioxadecalin-derived systems, axialequatorial rate ratios, 100-101 1,7-Dioxaspiro[5.5]undecane formation, acetal hydrolysis mechanism, 31-33 1,2-Disubstituted cyclohexanes, gauche effects, 127-129 Dominant interactions, pentaoxysulfuranes, 271*,272 Ε 2e~ stabilization and 4e~destabilization model of anomeric effect development, 162 origin of anomeric effect, 156,157/ splitting, 162-163 Edward, John T., history of anomeric effect postulation, 1-4 Edward-Lemieux effect, 7,22 Electron density, definition 162 Electrostatic component, anomeric and gauche effects, 126-152 Electrostatic effects anomeric effect, 57-61 description, 55-57 gauche effect, 63-68 reverse anomeric effect, 61-63 Endo and exo anomeric interactions for 2-substituted diheterocyclohexanes component analysis, 142,145*

Endo and exo anomeric interactions for 2-substituted diheterocyclohexanes— Continued experimental conformational free energies, 142,144* O-N interactions, 142,146-147 0 - 0 interactions, 142,145,147 reverse anomeric effect, 146 S-N interactions, 148 S-O interactions, 146,148 Endo anomeric effect, 8,132,133/ Energy analysis for neutral acetal systems energy decomposition model, 206-208* NH rotation model, 211-213* OH rotation model, 208-211 structures, 206-207 Energy analysis for protonated acetal systems energy decomposition model, 214*,215 NH rotation model, 217-219 OH rotation model, 215-217 Energy decomposition model analysis neutral systems of acetals, 206-208* protonated systems of acetals, 214*,215 Energy of system, definition, 162 Enzymic reactions, determination of transition-state geometry, 109-111 Epimeric pairs of tetrahydropyranyl derivatives antistereoelectronic behavior, 99 1,8-dioxadecalin-derived systems, generation or decomposition, 100-101 reaction profile, 98,99/ Eqec, definition, 258 Equatorial plane, definition, 258 Equatorial rotation of pentaoxysulfuranes using partially optimized torsional scan bond angle and length, 263,264* charges, 264,265* comparison with HOS0 , 262/263 energy, 261,262/ Escherichia coli β-galactosidase-catalyzed reactions, transition-state geometry, 110 Exo anomeric effect, 8,132,133/ 2

2

+

2

Fieser, role in anomeric effect postulation, 3 Fock matrix, regions in natural bond orbital basis, 161/


300



G β-Galactosidase-catalyzed reactions, transition-state geometry, 110 Gauche and anomeric effect interplay in substituted 1,4-diheterocyclohexanes additivity of orbital interactions, 149,151-152 equilibrium data, 144i,148 orbital interaction component, 145f,l 48-150r Gauche effect definition, 8,127 energy-level diagram through-space and through-bond orbital interactions, 129,131/ two-orbital, four-electron destabilizing orbital interaction, 129,130/ examples, 127-130 explanation, 63-68 Gauche effects in 5-substituted 1,3-diheterocyclohexanes component analysis, 136,138f Endo and exo anomeric interactions, 136 equilibrium data, 136,137i orbital interaction component analysis, 136,139-144 Geminal interactions, 267-269i Generalized anomeric effect, definition, 7-8 Geometry-dependent kinetic isotope effects, determination of transition-state geometry, 105-107 Glucopyranosyl derivatives bimolecularity of reactions, 102-105 kinetic isotope effects in reactions, 103f transition state, 104-105 transition-state geometry of nonenzymic reactions, 107-108 Glucopyranosylamines α and β anomers, equilibrium, 76,77i anomeric equilibrium, 72-73 C-NMR parameters, 75 free energy change for β to α anomer conversion, 76,77f Ή-NMR parameters, 73i-76 reverse anomeric effect, 78i,79 Glycoside(s), biomolecularity of reactions, 101-105 Glycoside cleavage ab initio studies with protonated dimeth oxymethane, 116,118-122 ,3

Glycoside cleavage—Continued advancement to transition state for cleavage of dimethoxymethane, 114 dimethoxymethane study, relevance to pyranosides, 123 hydrolysis of conformationally restrained pyranosides, 116,117/ sp vs. sp oxygen hybridization effect, 124/125 stereoelectronic control, 114-116 stereoelectronic requirements for cleavage, 123-124 Glycoside hydrolysis reaction coordinates and conformational changes, 43-44 substituent vs. rate, 45 transition state, 44-47 Glycoside(s) of N-acetylneuraminic acid, transition-state geometry of nonenzymic reactions, 108-109 Glycosidic angle, description, 278 Glycosyl transferring enzyme catalyzed reactions, determination of transitionstate geometry, 109-111 Glycosylmanganese complex insertion processes achimeric stabilization of transition state by C-2 alkoxy substituent, 232/ carbon-metal bond orientation vs. rate of migratory insertion, 235-238 migratory insertion, relative rates, 23It orientation of lone pairs ofringoxygen vs. rate of migratory insertion, 232-233,235 solution conformations of anomers, 233-235 structures, 230 2

3

H Hassel, anomeric effect postulation, 2-3 Haworth, W. N., role in anomeric effect postulation, 2 Hydrolysis conformationally restrained pyranosides, 116,117/ cyclic orthoesters, 47-53 glycosides, 30-47 Hydrolysis of tetrahydropyranyl derivatives, axial-equatorial rate ratios, 97-101


INDEX

301

Κ

η -» σ* interactions—Continued


Kinetic anomeric effect concept, 14-15 lack of evidence in acetal derivative reactions, 97-111 Kinetic isotope effects, geometry dependent, determination of transition-state geometry, 105-107 Kollman force field parameterization, O-C-N anomeric effect in nucleosides, 286-290 Kreevoy, anomeric effect postulation, 3 Kubo effect, definition, 22 L Lemieux, Raymond, role in anomeric effect postulation, 3 Lone pairs of electrons, role in anomeric and stereoelectronic effects, 11-12 Long-range transition states, stereoelectronic control of trigonal-bipyramidal phosphoesters, 248-250 M

glycoside cleavage ab initio studies with protonated dimeth oxymethane, 116,118-122 advancement to transition state for cleavage of dimethoxymethane, 114 dimethoxymethane study, relevance to pyranosides, 123 hydrolysis of conformationally restrained pyranosides, 116,117/ sp vs. sp oxygen hybridization effect, 124/125 stereoelectronic control, 114-116 stereoelectronic requirements for cleavage, 123-124 Natural atomic orbitals, concept, 161 Natural bond orbital analysis anomeric effect concept, 159-161 deletion energies, 163-165 electronic energies, 163-165 methodology, 173 NOSTAR geometries, 165-169 oxygen-centered pure-p lone pair interacting with antiperiplanar o* 158,159/ methyl-substituted sulfuranes, 273,274* pentaoxysulfuranes antibonding orbital populations, 265,266* bonding orbital populations, 265,266* description, 264 oxygen lone pair populations, 266,267* Natural orbitals, concept, 161 Neuraminidase-catalyzed reactions, transition-state geometry, 110-111 Neutral systems of acetals, energy analysis, 206-213 NH rotation model, energy analysis neutral systems of acetals, 211-213* protonated systems of acetals, 217-219 Nonenzymic reactions glucopyranosyl derivatives, determination of transition-state geometry, 107-108 glycosides of N-acetylneuraminic acid, transition-state geometry, 108-109 NOSTAR calculation, 165-169 Nucleosides atom numbering, 277-279/ 2

3

co>

Methoxy exchange, stereoelectronic control, 90-93/ 2-Methoxy-c/s-4,6-dimethyl-1,3-dioxanes, stereoelectronic control, 90-93/ 2-Methoxy-l,3dimethylhexahydropyrimidine, 80-81 Methyl ethylene phosphate, hydrolysis, 20 Methyl-substituted sulfuranes, 272,273* Methyl vinyl ether conformers atom electron populations, 201*,202 bond critical point properties, 202* component energies, 198,201* geometric bond lengths, 198* nonbonded charge concentrations, 184-198,202-203 Migratory insertion process, glycosylmanganese complexes, 230-238

Ν η —» σ* interactions bonding, See Bonding η —»σ* interactions

2


302


Nucleosides—Continued electron lone pairs of endocyclic oxygen, orientation, 280-282/ O-C-N anomeric effect, preliminary evidence, 281-283/ parameters describing conformations, 278,280 pseudorotation cycle of furanose ring, 278,279/ torsional angles, 277-279/


Ο O - C - N anomeric effect in nucleosides atom numbering, 277-279/ computational methods, 284-285 function, 277-278 Kollman force field parameterization, 286-290 parameters describing conformations, 278,280 primary evidence, 281-283/ pseudorotation cycle of furanose ring, 278,279/ pseudorotational potentials, 285-286,288-292 relationship to conformation, 280-282/ torsional angles, 277-279/ O-N interactions, Endo and exo anomeric interactions for 2-substituted diheterocyclohexanes, 142,146-147 O-O interactions, Endo and exo anomeric interactions for 2-substituted diheterocyclohexanes, 142,145,147 OAc groups, anomeric effects, 59-61 OAr groups, anomeric effects, 57-59 OH rotation model, energy analysis neutral systems of acetals, 208-211 protonated systems of acetals, 215-217 Oligosaccharides, roles in biochemical processes, 114 Orbital interaction component of 5-substituted 1,3-diheterocyclohexanes through-bond effects, 136,139,140/ through-bond σ —> afteractions, 139,141-144 through-space effects, 136,139,140/ Origin of anomeric effect comparison of interactions, 80-81

Origin of anomeric effect—Continued conformations studied, 157,158/ destabilization model, 156,157/ experimental description, 157,158/ geometric changes, 84 influencing factors, relative importance, 81,83i,84 n(O) -> a* interactions, 158-169 proposed explanations, 79-80 stabilization model, 156,157/ temperature effect on NMR spectrum, 81,82/ Orthoester hydrolysis antiperiplanar lone-pair hypothesis, 17-18 cyclic, 47-53 Ottar, role in anomeric effect postulation, 2 co

Ρ Pentaoxaphosphoranes, η —» σ* derealization, 257/ Pentaoxysulfuranes, stereoelectronic effects, 256-275 Phosphoryl transfer, stereoelectronic control, 19-22 Principle of least motion, arguments against validity for acetal hydrolysis mechanism, 41-43 Principle of least nuclear motion, 15 Protonated dimethoxymethane ab initio studies of glycoside cleavage, 116,118-122 advancement to transition state for cleavage, 119,123 Protonated systems of acetals, energy analysis, 214-219 Pseudorotational phase angle, description, 278,280 Pseudorotational potentials, O-C-N anomeric effect in nucleosides, 285-286,288,290-292 Pyranosides, conformationally restrained, hydrolysis, 116,117/ Q Quantitative modeling of anomeric effect correlation of four lone pair electrons, 169-172/


INDEX

303

Quantitative modeling of anomeric effect— Continued importance, 170,173 methodology, 173 Quantum theory of atoms in molecules, anomeric effect in dimethoxymethane calculation procedure, 203-204 conformers, 177-178 dimethoxymethane conformers, 179 experimental description, 177,179 methyl vinyl ether conformers, 180-203


R Reactivity of trigonal-bipyramidal phosphoesters, role of stereoelectronic effects in control, 240-254 Reeves, anomeric effect postulation, 2-4 Remote interactions, pentaoxysulfuranes, 271/,272 Repulsive gauche effect, definition, 127 Reverse anomeric effect bulky cationic substituent effect on conformational behavior, 72-79 definition, 8 description, 61 Endo and exo anomeric interactions for 2-substituted diheterocyclohexanes, 146 examples, 71 experimental evidence, 61-63 explanation, 70 Reverse anomeric studies in acetals energy analysis neutral systems, 206-213 protonated systems, 214-219 energy parameters, 223-225 π-bonding model NH systems, 221/,222 OH systems, 219-221 Ribonuclease, stereoelectronic control in phosphoryl transfer, 20-22 Rigid rotation of pentaoxysulfuranes bond orders, 258-261 energy, 258,259/ 2

S Second-order perturbational analysis of pentaoxysulfuranes dominant interactions, 271/,272

Second-order perturbational analysis of pentaoxysulfuranes—Continued geminal interactions, 267-269f vicinal interactions, 267-27It Sequential insertion processes condensation reaction, 229 C-glycosyl derivatives, 227-228 rate of manganocycle production vs. CO insertion into anomeric carbon-metal bond, 229-230 Shafizadeh, anomeric effect postulation, 3 S-N interactions, Endo and exo anomeric interactions for 2-substituted dihetero cyclohexanes, 148 S-0 interactions, Endo and exo anomeric interactions for 2-substituted dihetero cyclohexanes, 146,148 Spiro acetals formation mechanism, 31-33 transition states, 34-38 Stereoelectronic control description, 84 evidence, 85 methoxy exchange, 90-93/ predicted vs. experimental results for acetal derivatives, 97-111 test using cyclic amidine hydrolysis, 85-90 theory, 97 trigonal-bipyramidal phosphoesters bond angles and lengths, 242,244/,245/ CHELP charges, 242,247* dihedral angles, 242,246/ energies, 242,243/ experimental procedure, 242 long-range transition states, 248-250 Mulliken atomic charges, 242,247/ nomenclature, 242 phosphorane complexes from methyl ethylene phosphate alkaline hydrolysis, 250,251/ phosphorane complexes with basal NH group, 252-254 previous studies, 240-242 thermodynamic parameters, 242,243/ X - C - Y systems, identification, 240 Stereoelectronic effects applications, 6 control in phosphoryl transfer, 19-22 definitions, 7 structure and conformation, 7-14



304


Stereoelectronic effects—Continued transition-state structure and reactivity, 14-19 Stereoelectronic effects in hydrolysis acetal hydrolysis mechanism, 30-47 cyclic orthoester hydrolysis, 47-53 experimental evidence, 26-28,30 rate of hydrolysis, explanation using early transition state, 28-29 proposed hydrolysis pathways, 30 Stereoelectronic effects in pentaoxysulfuranes dominant intramolecular hydrogen bonding and vicinal charge transfer interactions, 275/ equatorial rotation using partially optimized torsional scan, 261-265 equatorial substitution effects, 272/-274* experimental procedure, 257,258/ future work, 275 natural bond orbital analysis, 264-267* pentaoxasulfurane trigonal bipyramidal structures, 258/ reaction scheme, 256,257/ rigid rotation, 258-261 second-order perturbational analysis, 267-272 Stereoelectronic stabilizing interactions, 6 Steric component, anomeric and gauche effects, 126-152 Structure of anomeric and stereoelectronic effects computational studies, 12-13 definition and clarification, 7-9 experimental evidence, 9-10 lone pairs of electrons, 11-12 second and third row effects, 13-14 theoretical rationale, 10-11 Structure of trigonal-bipyramidal phosphoesters, role of stereoelectronic effects in control, 240-254 Substituted diheterocyclohexanes conformational effects, 127-128 endo and exo anomeric interactions, 142,144-148 gauche effects, 129-130 interplay of anomeric and gauche effects, 144,148-152 5-Substituted 1,3-dioxanes, attractive gauche effect, 127-128 Sulfate esters, reaction scheme, 256,25'yf f

Sulfuryl group transfer, 256-275 Syn and ±synclinal, description, 278 Synperiplanar lone-pair hypothesis, 16,18

Τ Taft, role in anomeric effect postulation, 3 Tetrahydropyranyl derivatives, axialequatorial rate ratios in hydrolysis, 97-101 Thompson, anomeric effect postulation, 3 Through-bond effects, orbital interaction component of 5-substituted 1,3-diheterocyclohexanes, 136,139,140/ Through-bond σ —> ^interactions, orbital interaction component of 5-substituted 1,3-diheterocyclohexanes, 139,141 -144 Through-space effects, orbital interaction component of 5-substituted 1,3-dihetero cyclohexanes, 136,139,140/ Transition-state geometry determination from geometry-dependent kinetic isotope effects, 105-107 enzymic reactions, 109-111 nonenzymic reactions glucopyranosyl derivatives, 107-108 glycosides of N-acetylneuraminic acid, 108-109 Transition-state structure and reactivity, anomeric and stereoelectronic effects acetal hydrolysis, 16 acetal oxygen basicity, 16 amidine hydrolysis, 17-18 antiperiplanar lone-pair hypothesis, 14-19 orthoester hydrolysis, 17-18 principle of least nuclear motion in acetals, 15 synperiplanar lone-pair hypothesis, 16 Trigonal-bipyramidal phosphoesters, role of stereoelectronic effects in control of structure and reactivity, 240-254 3,7,9-Triheterobicyclo[3.3.1]nonanes, lonepair interactions, 129-130 V Vibrio cholerae neuraminidase catalyzed reactions, transition-state geometry, 110-111 Vicinal interactions, 267-271*


INDEX

305 Y

X - C - Z anomeric effect endo and exo anomeric effects, 132,133/ endo and exo interactions, 142,144-148 interplay with gauche effects, 144,148-152 methodology, 132,134-135 3-X-substituted 1,5-benzodioxepins, confor mational study, 129,131

Y - C - C - Z gauche effect attractive and repulsive effects, 127-133 interplay with anomeric effects, 144,148-152 methodology, 132,134-135 orbital interaction component, 136,139-144


Χ


The Anomeric Effect and Associated Stereoelectronic Effects

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