B 109

INDEX

Downloaded by 203.64.11.45 on September 24, 2016 | http://pubs.acs.org Publication Date: January 25, 1979 | doi: 10.1021/bk-1979-0087.ix001

A

AGO isomers for the a-glucoside 27 A Q T isomers for the a-glucoside 27 A b initio Hartree-Fock 431-G calculations on dimethoxymethane 53 molecular-orbital calculations on methanediol 18 quantum-mechanical calculations .. 52 S T O - 3 G wavefmiction calculation .. 1 Acetal geometry in methyl a-D-pyranosides 55 geometry in methyl 0-D-pyranosides 56 moiety in pyranosides 54 moiety in pyranoses 54 Aglycon(s) hydrocarbon 19 importance of exo-anomeric effect to the orientation of 22 frans-2-R-methylcyclohexyl 20 frans-S-methylcyclohexyl 20 per-O-acetyl methyl glycosides with equatorial 11 -sugar interactions 30 Alcohol on alpha selectivity in glycosi dations, influence of 83 Alcohol concentration and a-stereospecificity 84 Aldopyranose anomers 11 2-Alkoxytetrahydropyrans, anomeric effect in .. 95 Alkyl D-glycopyranosides assuming JC'H 11 eos -Arabino derivatives 66,75 0-Arabino derivatives 5 /?-D-Arabino configurations, compari son of per-O-acetylated glycopyranosyl halides with 7 /3-D-Arabino derivatives 66 D-Arabinofuranosyl halides, methanolysis of anomeric 82 /?-D-Arabinopyranose derivatives 73 Arylsulfonate stereoselectivity 88 Attractive effect, gauche 101 Axial bonds, p values for 10 C - C l bond, interactions in glycopyranosyl halides with 14 C - l - H bond 11 chlorides, resonance frequencies of 6 chlorine, orbital population on 5 conformation 1

B Benzoates, conformational analysis of pentopyranosyl 2-O-Benzyl-l-O-tosyl-D-galactopyranose 2-O-Benzy 1- 1-O-tosyl-D-glucopyranose Bisected conformations of an a-chloroanion

109

Szarek and Horton; Anomeric Effect ACS Symposium Series; American Chemical Society: Washington, DC, 1979.

63 90 90 13

ANOMERIC E F F E C T


110 Bond(s) axial C - l - H a carbon-chlorine P carbon-chlorine equatorial C - l - H lengths of a-anomer of /?-anomer of dimethoxymethanol model C-O of methoxymethanol model C - O in per-O-acetylated hexopyranosyl chlorides shortening of anomeric C - l - O H .. p values for axial p values for equatorial s character of the carbon atom of C - H s character of the C - H equatorial .. cr-Bonds, interaction between oxygen p-type lone pair and adjacent

11 5 5 11 21 21 59 59 6 58 10 10 9 10 12

C C - H bonds in conformers of 2-chlorotetrahydropyran C - H bonds, s character of the carbon atom of C - H equatorial bond, s character of .. C 1 N Q R frequencies of per-O-acetyl ated glycopyranosyl chlorides, distribution of C 1 N Q R frequencies in per-O-acetyl ated hexapyranosyl chlorides ...... Carbon atom ot C - H bonds, s char acter of a Carbon-chlorine bonds fi Carbon-chlorine bonds Carbon-13 hydrogen direct coupling constants Chloride(s) derivatives, pentopyranosyl penta-O-acetyl-a-D-idopyranosyl .... per-O-acetylated glycopyranosyl .... resonance frequencies or axial tetra-O-acetyl-^-D-xylopyranosyl .... Chlorine, orbital population on axial.. Chlorine, orbital population on equatorial a-Chloroanion bisected conformations of eclipsed conformations of molecular-orbital calculations for .... 2-Chlorotetrahydropyran C - H bonds in contormers of calculation of molecular orbitals of conformations of H O M O of

g Q ,Q

35

1

4

35

r% 0

q 2 g

6 9

o

n

^ 1 J* 2 2 ,

M/n-Clinal orientation 17 Conformation (s) axial 1 ^ ( L ) 3 ^(D) 3 of 2-cnlorotetrahydropyran 3 equatorial 1 gauche 96 Conformational analysis of heterocyclic compounds 80 analysis of pentopyranosyl acetates 63 benzoates 63 halides 63 assignment of 5-methoxy-l,3dithianes 99 control of the exo-anomeric effect... 30 equilibrium of 1,2-disubstituted cyclohexanes 97 importance of the anomeric effect .. 30 interactions in 1,4-heterobutane segments 95 Conformers of 2-chlorotetrahydropyran, C - H 6 Coupling constants, carbon-13 nydrogen direct 6,8 Crystalline equatorial states 71 Cyclohexyl o-D-glucopyranosides, substituted 24 Cyclohexyl /?-D-glucopyranosides, substituted 24 C - c h a i r conformation 30 ^ ( L ) conformations 3 C I ( D ) conformations 3 C-l in furanose sugars (anomeric carbon atom) 50 - H bond, axial 11 - H bond, equatorial 11 - O H bond length, shortening of the anomeric 58 in pyranose sugars, anomeric carbon atom 50 p-toluenesulfonates 89 C - C l bond 1 interactions in glucopyranosyl halides with axial 14 C - O bond lengths of dimethoxymethanol model 59 C - O bond lengths of methoxymethanol model 59

0

1 6 2 3 13

4

4

Deacetylation of trans,trans-2 6-dimethylcyclohexyl-l- C tetra-Oacetyl-^-D-glucopyranoside Destabilization of the equatorial conformer y

13


26 80

111

INDEX 1,3-Diaxial disposition, ring-oxygen atom in 1,3-Diaxial interaction(s)

(Pa, a)

G 75 67,73 39 74 70

possible Diequatorial ( C i ) form .. 2,6-Dimethylcyclohexyl o-D-glucopyranoside trans, *rans-2,6^Dimethylcyclohexyl1- C tetra-O-acetyl-^-n-glucopyranoside, deacetylation of ...... Dimethoxymethane, ab initio HartreeFock 431-G calculations on Dimethoxymethane model Dimethoxymethanol ( C H O C H OCH ) Dimethoxymethanol model, C - O bond lengths of Dipole -dipole interaction -dipole relaxation mechanism internuclear relaxation contribution, 4

23

13


3

26 53 60

2

3

59 59 11 31

p(j->i) • • • 40 Direct coupling constants, carbon-13 hydrogen 6,8 trans- 1,2-Disubstituted cyclohexanes, conformational equilibrium of .... 97 1,5-Dithio-pyranosides 51 E Eclipsed conformations of an a-chloroanion 13 Electronegative difference, Pauling's .. 50 Electrons, lone-pair 50 Equatorial aglycon, per-O-acetyl methyl glycosides with 11 bond, 5 character of the C - H 10 bonds, p values for 10 C - l - H bond 11 chlorine, orbital population on 5 conformation 1 conformer, destabilization of 80 states, crystalline 71 Equilibrium glycosidation of Fischer 80 Ethers, stereoselectivity of 89 Excess repulsion 101 Exo-anomeric effect 17,28,51 conformational control of 30 to the orientation of an aglycon, importance of 22 F Fischer, equilibrium glycosidation of Fluoride derivatives, pentopyranosyl Furanose sugars, anomeric carbon atom ( C - l ) in

80 30 50

A G for equilibrations 100 Galactopyranose residue, ring protons of 39 Gauche conformation 96 effects 51,96,98 attractive 101 repulsive 97,101,102 interactions ( p ) 39 a-D-Gluco configurations, comparison of per-O-acetylated glycopyranosyl halides with 7 D-Glucose derivatives 8 o-Glucoside, A T and A isomers for 2 7 £-Glucosides 25 Glycopyranosyl halides with axial C - C l bond, interactions in 14 a-D-Glucopyranosyl, metal-assisted glycosidation of 85 /?-D-Glucopyranosyl- (1 - » 6 ) -Dgalactopyranose, synthesis of 42 Glycosidation(s) of a-D-glucopyranosyl, metalassisted 85 halide-ion-catalyzed 84 influence alcohol on alpha selectivity in .... 8 3 halide-ion concentration on alpha selectivity in 83 solvents on alpha selectivity in .... 9 0 substituents on alpha selectivity in 9 0 mechanism of 82 reactions, stereoselectivity of 88 on 1-O-tosyl-D-mannopyranose derivatives, rapid 91 ^-Glycosidations, solvent properties significant in 87 Glycoside(s) with equatorial aglycon, per-Oacetyl methyl 11 formation, stereoselectivity of 84 -forming reactions 80 synthesis 80 influence of reactant structure on 8 0 influence of solvent on 80 a-Glycoside(s) 86 synthesis 86 ci.?-l,2-Glycosides 81 fTtfrw-l,2-Glycosides 81 Glycosidic linkages 18 Glycosyl derivatives 81 0

g

QG

G

H ' H N M R spectra of methyl 0-Dglucopyranoside 36,37 H - l resonance relaxation contribution 4 4



112

ANOMERIC EFFECT

H-5 resonance relaxation contribution Halide(s) with ^-D-arabino configurations, comparison of per-O-acetylated glycopyranosyl conformational analysis of pento pyranosyl with tt-D-gluco configurations, com parison of per-O-acetylated glycopyranosyl -ion-catalyzed glycosidation -ion concentration on alpha selec tivity in glycosidations, influ ence of with a-D-ribo configurations, com parison of per-O-acetylated glycopyranosyl halides with /?-D-xylo configurations, com parison of per-O-acteylated glycopyranosyl a-Haloethers, N Q R frequencies of Hammett substituent constants Hard-sphere calculations nonbonded interactions estimated by Hartree-Fock 431-G calculations on dimethoxymethane, ab initio Hemi-acetal geometry in a-n-pyranose Hemi-acetal moiety in pyranoses and pyranosides 1,4-Heterobutane segments, conforma tional interactions in Heterocyclic compounds, conforma tional analysis of Hexopyranosyl derivatives Highest occupied molecular orbital (HOMO) of 2-chlorotetrahydropyran H O M O (see Highest occupied molecular orbital) Hydrocarbon aglycons Hydrogen -bonding capacity chemical reactivity at anomeric direct coupling constants, carbon-13

I Interproton distances determined by proton relaxation measurement Isomers for the a-glucoside, A Q T and AQT

•

cis-Isomer trans-Isomer Isomeric pentose derivatives

K

44 Karplus curve Karplus relationship

27 27

7 63

7 84

L Lone-pair electrons Lone pairs, ring-oxygen p-type in pyranose derivatives Lucken-Altona theory a-D-Lyxo derivative £-D-Lyxo derivative

50 10 1 10 75 75

83 M 7

Manno compounds 6 a-Mannopyranoside selectivity of compounds with nonparticipating 7 substituents on C-2 92 12 Mannopyranosyl derivatives 92 84 Metal-assisted glycosidation of O-D23 glucopyranosyl 85 Methanediol, ab initio molecular24 orbital calculations on 18 Methanolysis of anomeric D-arabino53 furanosyl halides 82 57 5-Methoxy-l,3-dithianes, configura tional assignment of 99 54 5-Methoxy-l,3-dithianes, synthesis of 98 Methoxymethanol ( C H O C H O H ) .. 59 95 Methoxymethanol model, C - O bond lengths of 59 17 80 2-Methoxytetrahydropyran 35 3 Methyl 0-D-glucopyranoside m N M R spectra of 36,37 58 10 Methyl a-pyranosides acetal geometry in 55 13 Methyl ^-pyranosides 58 acetal geometry in 56 frans-2-R-Methylcyclohexyl aglycon .. 20 19 frans-S-Methylcycfohexyl aglycon 20 2-fl-Methylcyclohexyl a-D-gluco87 pyranoside 19 10 2-S-Methylcyclohexyl 0-D-gluco6,8 pyranoside 19 frarw-2-Methylcyclohexyl a-D-glycopyranosides 27 frarw-2-Methylcyclohexyl 0-D-glycopyranosides 27 33 Methylthio compounds, synthesis of .. 99 47 5-( Methylthio) -1,3-dithianes, synthesis of 99 27 Molecular-orbital calculations on methanediol, ab initio 18 98 98 Molecular orbitals of 2-chlorotetra hydropyran, calculation of 2 73 8

2


INDEX Monosaccharides, configurational dependence for anomeric protons of

30

N Nickel, Raney Nonbonded interactions estimated by hard-sphere calculations Nonselective relaxation rate (Ri (ns)) for /J-D-glucopyranosyl- (1 -> 6)-Dgalactopyranose 6,6-di-deuterio analog N Q R (see Nuclear Quadruple Resonance) Nuclear Quadruple Resonance ( N Q R ) frequencies of a-haloethers of per-O-acetylated glycopyranosyl chlorides, distribution of C 1 in per-O-acetylated hexapyranosyl chlorides, ^ l


A

M

26 24 34 46 46

3 12 4 6

O O - C a* orbital O / O anomeric effect Orbital population on axial chlorine .. Orbital population on equatorial chlorine Outward bending in spirobicycles Oxygen p-type lone pair and adjacent cr-bond, interaction between

51 95 5 5 104 12

P p-type lone pairs, ring-oxygen Pauling's electronegative difference ... Penta-O-acetyl-a-D-idopyranosyl chloride Pentopyranosyl acetates, conformational analysis of benzoates, conformational analysis of chloride derivatives derivatives in solution fluoride derivatives halides, conformational analysis of .. Pentose derivatives, isomeric Per-O-acetyl methyl glycosides with equatorial aglycon Per-O-acetylated glycopyranosyl chlorides bond lengths ^ C l " N Q R frequencies in distribution of the ^ l N Q R frequencies of

10 50

Per-O-acetylated glycopyranosyl halides, comparison with 0-n-arabino configurations o-r>gluco configurations /?-D-ribo configurations a-D-xylo configurations Proton(s) of monosaccharides, configurational dependence for anomeric relaxation measurement, interproton distances determined by spin-lattice relaxation rates (Ri-values) Pulse Fourier transform methods Pyranose(s) acetal moiety in derivatives, ring-oxygen p-type lone pair in derivatives, ring-oxygen or-bonds in hemi-acetal moiety in sugars, anomeric carbon atom ( C - l ) in structural properties of the anomeric center in 5-thioa-D-Pyranose, hemi-acetal geometry in a-Pyranose sugars /?-Pyranose sugars Pyranoside(s) acetal geometry in methyl «-r>geometry in methyl £-r> moiety in 1,5-dithiohemi-acetal moiety in structural properties of the anomeric center in a-Pyranosides, methyl 0-Pyranosides, methyl

3

63 30 Jj

Quadruple Resonance, Nuclear ( N Q R ) frequencies Quantum-mechanical calculations, ab initio

73 11 3 6 6 4

R R i values (proton spin-lattice relaxation rates) R (ns) (nonselective relaxation rate) R i ( A ) (single-selective relaxation rate) Raney nickel X

A

A


ANOMERIC E F F E C T


114 Rapid glycosidations on l-O-Tosyl-Dmannopyranose derivatives 91 Reactant structure on glycoside synthesis, influence of 80 Reactions, glycoside-forming 80 Regressional analysis 35 Relaxation contribution(s) 43 H - l resonance 44 H-5 resonance 44 p(j -> i ) , dipole 40 measurement, interproton distances determined by proton 47 mechanism, dipole-dipole 31 process of spin-lattice 31 proton spin-lattice 30 rate(s) ( R i values), proton spin-lattice .. 30 R / (ns)), nonselective 34 R i (A)), single-selective 34 time measurement using a twopulse sequence, spin-lattice 32 Repulsion, excess 101 Repulsive Gauche effect 97,101,102 Resonance frequencies of axial chlorides 6 Resonance, Nuclear Quadruple ( N Q R ) frequencies 3 Rhamno compounds 6 Ribo compounds, ring-torsional angles of 70 Ribo derivatives 69 o-D-Ribo compounds 72 £-Ribo compounds 72 ^-D-Ribo configurations, comparison of per-O-acetylated glycopyran osyl halides with 7 £-D-Ribo derivative 5 Ring -oxygen atom in 1,3-diaxial disposition .... 75 Torsion angles of glycopyranosides 1-O-Tosyl-D-mannopyranose deriva tives, rapid glycosidations on Townes and Dailey formula Transform methods, pulse Fourier .... 3,4,6-Tri-O-benzyl-l-O-p-tolylsulfonyl-D-mannopyranose Triequatorial form Two-pulse sequence, spin-lattice relaxation time measurement using H


33 5 68 51 89 23 27 91 3 30 92 70

32

115

INDEX V Valence-bond angles about the anomeric center p-Value(s) for axial bonds for equatorial bonds measurement

23

X-ray crystal-structure determinations

18

35

X-ray structure analysis

63

10 10 35

0-Xylo compounds ring-torsional angles of a-D-Xylo configurations, comparison of per-O-acetylated glycopyran osyl halides with a-D-Xylopyranose derivative

73 70

1


W Wavefunction calculation, ab initio STO-3G

X


7 73

B 109

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