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Mechanisms For Nucleophilic Aliphatic Substitution At Glycosides

N. Horenstein
Published 2006 · Chemistry

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Abstract Much of carbohydrate chemistry and biochemistry is centered on bond forming and bond breaking reactions at the anomeric carbon of glycosides. No single mechanism adequately covers the scope of these reactions, because differences in sugar substituents, stereochemistry, leaving groups, nucleophiles, and catalysts can influence the mechanistic pathway taken. The influence of solvent is only now beginning to become apparent in greater detail. Several methods exist to probe the mechanisms of these reactions; they include a variety of kinetic studies, including isotope effects, and computational methods. It has been found that typical reactions will uniquely utilize a mechanism somewhere within a continuum between A N D N and D N +A N mechanisms. With knowledge of the factors that determine the mechanism, synthetic method development will be furthered and a deeper understanding of biological catalysis is likely to be gained.
This paper references
10.1016/S0065-3160(02)37004-7
Transition State Analysis Using Multiple Kinetic Isotope Effects: Mechanisms of Enzymatic and Non-enzymatic Glycoside Hydrolysis and Transfer
P. Berti (2002)
10.1021/JA00148A002
HYDROLYSIS OF (2-DEOXY-BETA -D-GLUCOPYRANOSYL)PYRIDINIUM SALTS
X. Huang (1995)
10.1021/JA050830I
Structural evidence that alkoxy substituents adopt electronically preferred pseudoaxial orientations in six-membered ring dioxocarbenium ions.
S. Chamberland (2005)
10.1038/nrd1751
Glycans in cancer and inflammation — potential for therapeutics and diagnostics
Danielle H Dube (2005)
10.1002/ANIE.200453688
Mechanism of 4,6‐O‐Benzylidene‐Directed β‐Mannosylation as Determined by α‐Deuterium Kinetic Isotope Effects
D. Crich (2004)
10.1021/JA00085A065
EXOCYCLIC AND ENDOCYCLIC CLEAVAGE OF PYRANOSIDES IN BOTH METHANOL AND WATER DETECTED BY A NOVEL PROBE
J. Liras (1994)
10.1021/JA047578J
The disarming effect of the 4,6-acetal group on glycoside reactivity: torsional or electronic?
H. Jensen (2004)
10.1016/J.SBI.2004.08.006
Carbohydrate-carbohydrate interactions in cell recognition.
I. Bucior (2004)
10.1002/JMS.880
Formation and stability of oxocarbenium ions from glycosides.
C. Denekamp (2005)
10.1021/CR040461T
Toward a detailed understanding of base excision repair enzymes: transition state and mechanistic analyses of N-glycoside hydrolysis and N-glycoside transfer.
P. Berti (2006)
10.1002/CHEM.200400773
Aspects of glycosidic bond formation in aqueous solution: chemical bonding and the role of water.
J. Stubbs (2005)
10.1021/JO0004106
Solvolyses of 2-Deoxy-α- and β-d-Glucopyranosyl 4‘-Bromoisoquinolinium Tetrafluoroborates
Jiang Zhu (2000)
10.1021/JA00202A033
Lifetimes of oxocarbenium ions in aqueous solution from common ion inhibition of the solvolysis of α-azido ethers by added azide ion
T. L. Amyes (1989)
10.1021/JA00052A011
Pathways for the hydrolysis of glycosides of N-acetylneuraminic acid
M. Ashwell (1992)
10.1039/B108446C
Mechanisms of glycopyranosyl and 5-thioglycopyranosyl transfer reactions in solution
A. Bennet (2002)
10.1021/JA9813055
Spontaneous Hydrolysis of Glycosides
R. Wolfenden (1998)
10.1021/JA00021A021
Reactions of anionic nucleophiles with .alpha.-D-glucopyranosyl fluoride in aqueous solution through a concerted, ANDN (SN2) mechanism
N. Banait (1991)
10.1021/JA961811Z
Acid-Catalyzed Solvolysis of CMP-N-Acetyl Neuraminate: Evidence for a Sialyl Cation with a Finite Lifetime
B. Horenstein (1996)
10.1016/J.CARRES.2004.12.021
The two-conformer hypothesis: 2,3,4,6-tetra-O-methyl-mannopyranosyl and -glucopyranosyl oxacarbenium ions.
T. Nukada (2005)
10.1021/JA01465A035
Salt Effects and Ion Pairs in Solvolysis and Related Reactions. XVII.1Induced Common Ion Rate Depression and the Mechanism of the Special Salt Effect2-4
S. Winstein (1961)
10.1039/JR9610003240
636. Mechanism of reactions in the sugar series. Part IV. The structure of the carbonium ions formed in the acid-catalysed solvolysis of glucopyranosides
B. Banks (1961)
10.1021/JA992044H
The Role of Sugar Substituents in Glycoside Hydrolysis
M. Namchuk (2000)
10.1021/JA0394028
Probing the transition states of four glucoside hydrolyses with 13C kinetic isotope effects measured at natural abundance by NMR spectroscopy.
J. K. Lee (2004)
10.1002/POC.526
Experimental and computational studies of α‐lactones: Structure and bonding in the three‐membered ring
J. Buchanan (2002)
10.1021/JA972503J
The N-Acetyl Neuraminyl Oxecarbenium Ion Is an Intermediate in the Presence of Anionic Nucleophiles
B. Horenstein (1998)
10.1021/JA00004A066
Torsional effects in glycoside reactivity: saccharide couplings mediated by acetal protecting groups
B. Fraser-Reid (1991)
10.1016/0040-4020(94)01019-V
A consideration of the barrier for carbocation-nucleophile combination reactions
J. Richard (1995)
10.1021/OL030081E
Steric effects are not the cause of the rate difference in hydrolysis of stereoisomeric glycosides.
H. Jensen (2003)
10.1021/BI000061+
Primary 13C and β-Secondary 2H KIEs for Trans-sialidase. A Snapshot of Nucleophilic Participation during Catalysis†
J. Yang (2000)
10.1002/1521-3765(20020301)8:5<1218::AID-CHEM1218>3.0.CO;2-X
Stereoelectronic substituent effects in polyhydroxylated piperidines and hexahydropyridazines.
H. Jensen (2002)
10.1002/JMS.848
Anomeric distinction and oxonium ion formation in acetylated glycosides.
C. Denekamp (2005)
10.1021/ja00526a043
Solvolysis of D-glucopyranosyl derivatives in mixtures of ethanol and 2,2,2-trifluoroethanol
M. Sinnott (1980)
10.1021/JO00312A004
Armed/disarmed effects in glycosyl donors: rationalization and sidetracking
B. Fraser-Reid (1990)
10.1021/JA00029A008
Molecular mechanical investigations of the properties of oxocarbenium ions. 2. Application to glycoside hydrolysis
R. Woods (1992)
10.1021/JA047476T
Conformational effects on glycoside reactivity: study of the high reactive conformer of glucose.
C. McDonnell (2004)
10.1021/JO00952A047
Bis(trifluoromethyl)acetolactone, a Stable a-Lactone'
W. Adam (1973)
10.1021/CR60260A001
Mechanism in carbohydrate chemistry
B. Capon (1969)
10.1021/JO0205356
Equatorial contra axial polar substituents. The relation of a chemical reaction to stereochemical substituent constants.
M. Bols (2002)
10.1021/JA973945Y
Hydrolysis of (2-Deoxy-α-d-Glucopyranosyl)pyridinium Salts: The 2-Deoxyglucosyl Oxocarbenium Is Not Solvent-Equilibrated in Water
J. Zhu (1998)
10.1021/JO00092A021
Reactions of charged substrates. II: Gas-phase dissociation of 2'-substituted nicotinamide arabinosides
Neil Buckley (1994)
10.1021/JA00015A056
Absence of nucleophilic assistance by solvent and azide ion to the reaction of cumyl derivatives: mechanism of nucleophilic substitution at tertiary carbon
J. Richard (1991)
10.1021/JA00317A034
General base catalysis of the addition of hydroxylic reagents to unstable carbocations and its disappearance
J. Richard (1984)
10.1021/JA981041M
Exploring the Mechanism of Neighboring Group Assisted Glycosylation Reactions
T. Nukada (1998)
10.1016/J.STR.2004.02.036
Structural insights into the catalytic mechanism of Trypanosoma cruzi trans-sialidase.
M. F. Amaya (2004)
10.1021/JA001641X
Effect of Neutral Pyridine Leaving Groups on the Mechanisms of Influenza Type A Viral Sialidase-Catalyzed and Spontaneous Hydrolysis Reactions of α-d-N-Acetylneuraminides
D. H. Chou (2000)
10.1021/JO970677D
Experimental and Theoretical Evidence of Through-Space Electrostatic Stabilization of the Incipient Oxocarbenium Ion by an Axially Oriented Electronegative Substituent During Glycopyranoside Acetolysis
M. Miljkovic̄ (1997)
10.1021/JA01642A079
The Synthesis of Glucofuranosides
D. Phillips (1954)
10.1021/JA00096A012
Kinetic Isotope Effect Study of Transition States for the Hydrolyses of .alpha.- and .beta.-Glucopyranosyl Fluorides
Yulei Zhang (1994)
10.1016/S0065-3160(04)39001-5
Dynamics for the reactions of ion pair intermediates of solvolysis
J. Richard (2004)
10.1021/AR970172+
Glycosidase mechanisms: anatomy of a finely tuned catalyst.
D. Zechel (2000)
10.1021/JA037935A
Stereochemistry of nucleophilic substitution reactions depending upon substituent: evidence for electrostatic stabilization of pseudoaxial conformers of oxocarbenium ions by heteroatom substituents.
Leticia Ayala (2003)
10.1111/J.1432-1033.1984.TB08087.X
Chemical behaviour of cytidine 5'-monophospho-N-acetyl-beta-D-neuraminic acid under neutral and alkaline conditions.
J. M. Beau (1984)
10.1021/CR980007N
Carbanionic reactivity of the anomeric center in carbohydrates.
L. Somsák (2001)
10.1021/AR00166A001
IUPAC recommendations for the representation of reaction mechanisms
R. Guthrie (1989)
10.1016/S0008-6215(02)00043-5
Can the stereochemical outcome of glycosylation reactions be controlled by the conformational preferences of the glycosyl donor?
T. Nukada (2002)
10.1002/POC.789
Time‐resolved IR studies of α‐lactones
B. M. Showalter (2004)
10.1021/OL036220+
Hydrolysis of alpha- and beta-glycosides. New experimental data and modeling of reaction pathways.
P. Deslongchamps (2004)
10.1021/JA00031A068
Exo and endo activation in glycoside cleavage: acetolysis of methyl .alpha.- and .beta.-glucopyranosides
D. McPhail (1992)
10.1021/JA00283A025
Complete kinetic isotope effect description of transition states for acid-catalyzed hydrolyses of methyl .alpha.- and .beta.-glucopyranosides
A. Bennet (1986)
10.1021/OL0500620
Investigations into the role of ion pairing in reactions of heteroatom-substituted cyclic oxocarbenium ions.
Siddhartha R Shenoy (2005)
10.1002/POC.776
Aqueous methanolysis of an α-D-N-acetylneuraminyl pyridinium zwitterion: solvolysis occurs with no intramolecular participation of the anomeric carboxylate group†
Tara L. Knoll (2004)
10.1021/JA0344967
Trypanosoma cruzi trans-sialidase operates through a covalent sialyl-enzyme intermediate: tyrosine is the catalytic nucleophile.
A. Watts (2003)
10.1021/JA035600N
Glycosidic bond formation in aqueous solution: on the oxocarbenium intermediate.
J. Stubbs (2003)
10.1016/S0065-2318(04)59003-0
Synthesis and reactions of glycosides.
P. Garegg (2004)
10.1080/01442350500415107
Sugars in the gas phase. Spectroscopy, conformation, hydration, co-operativity and selectivity
J. Simons (2005)
10.1021/CR60291A004
Mechanism and catalysis for hydrolysis of acetals, ketals, and ortho esters
E. Cordes (1974)
10.1021/JA963807T
The Ratio between Endocyclic and Exocyclic Cleavage of Pyranoside Acetals Is Dependent upon the Anomer, the Temperature, the Aglycon Group, and the Solvent
J. Liras (1997)
10.1039/B204132D
Sugars in the gas phase: the spectroscopy and structure of jet-cooled phenyl β-D-glucopyranoside
F. Talbot (2002)
10.1039/B300626C
Sugars in the gas phase
R. A. Jockusch (2003)
10.1021/JA042280E
Unexpected stability of aryl beta-N-acetylneuraminides in neutral solution: biological implications for sialyl transfer reactions.
V. Dookhun (2005)
10.1016/J.THEOCHEM.2003.09.006
Theoretical studies of the mechanism of the Brönsted-acid-catalyzed glycosidation of α- and β-d-glucofuranurono-6,3-lactone
A. Nowacki (2003)



This paper is referenced by
Influence Of Side Chain Conformation On The Mechanism(s) Of Glycosylation Reactions; Investigation Of Sialidation Reaction Mechanism(s) By Kinetic Studies
H. C. Amarasekara (2019)
10.1021/jacs.6b06943
Borinic Acid Catalyzed Stereo- and Regioselective Couplings of Glycosyl Methanesulfonates.
Kyan A D'Angelo (2016)
10.1021/jo2017026
Methodology development and physical organic chemistry: a powerful combination for the advancement of glycochemistry.
D. Crich (2011)
10.1021/jo201179p
Stereoselective synthesis of 2,3-diamino-2,3-dideoxy-β-D-mannopyranosyl uronates.
Marthe T. C. Walvoort (2011)
10.1016/j.carres.2010.01.023
Selective formation of glycosidic linkages of N-unsubstituted 4-hydroxyquinolin-2-(1H)-ones.
Roman Kimmel (2010)
10.1002/CHIN.200829276
Mechanisms for Nucleophilic Aliphatic Substitution at Glycosides
N. Horenstein (2008)
10.1080/07328303.2011.624284
Mannuronic Acids: Reactivity and Selectivity
Jeroen D. C. Codée (2011)
10.1021/ar100035r
Mechanism of a chemical glycosylation reaction.
D. Crich (2010)
10.1021/ol2016862
Mannopyranosyl uronic acid donor reactivity.
Marthe T. C. Walvoort (2011)
10.1016/J.TET.2007.03.128
β-Selective Glucosylation in the Absence of Neighboring Group Participation: Influence of the 3,4-O-Bisacetal Protecting System.
D. Crich (2007)
10.1016/J.CPLETT.2012.08.033
O-Glycosidic bond exocyclic cleavage of difructose led by acidic proton migration: Density functional theory calculation study
Po-Tuan Chen (2012)
Prebiotic synthesis of nucleic acids
H. Bean (2008)
10.1038/nchem.1404
Dissecting the Mechanisms of a Class of Chemical Glycosylation Using Primary 13C Kinetic Isotope Effects
M. Huang (2012)
10.1021/jacs.5b06126
Cation Clock Reactions for the Determination of Relative Reaction Kinetics in Glycosylation Reactions: Applications to Gluco- and Mannopyranosyl Sulfoxide and Trichloroacetimidate Type Donors.
Philip O. Adero (2015)
10.1016/BS.APOC.2017.09.001
Probing Transition State Analogy in Glycoside Hydrolase Catalysis
C. Colombo (2017)
10.1016/j.carres.2010.01.005
N,N-Diacetylsialyl chloride--a novel readily accessible sialyl donor in reactions with neutral and charged nucleophiles in the absence of a promoter.
A. V. Orlova (2010)
10.1021/ja307266n
Cation clock permits distinction between the mechanisms of α- and β-O- and β-C-glycosylation in the mannopyranose series: evidence for the existence of a mannopyranosyl oxocarbenium ion.
M. Huang (2012)
10.1002/anie.201204400
Dissecting the influence of oxazolidinones and cyclic carbonates in sialic acid chemistry.
Pavan K. Kancharla (2012)
10.1021/jo3011655
Stereoselective C-glycoside formation with 2-O-benzyl-4,6-O-benzylidene protected 3-deoxy gluco- and mannopyranoside donors: comparison with O-glycoside formation.
Myriame Moumé-Pymbock (2012)
10.1016/J.CRCI.2010.03.016
A propos of glycosyl cations and the mechanism of chemical glycosylation
L. Bohé (2011)
10.1016/j.carres.2010.02.027
The impact of oxacarbenium ion conformers on the stereochemical outcome of glycosylations.
M. T. Walvoort (2010)
10.1016/J.TETLET.2009.12.109
Hydroxyl group orientation affects hydrolysis rates of methyl α-septanosides
Shankar D. Markad (2010)
10.1016/J.TET.2011.09.059
Substituent effects in endocyclic cleavage–recyclization anomerization reaction of pyranosides
Shino Manabe (2011)
10.1039/c2ob25451d
Direct participation of counter anion in acid hydrolysis of glycoside.
Hung Duy Phan (2012)
10.1039/C6OB02263D
Bent bonds (τ) and the antiperiplanar hypothesis, and the reactivity at the anomeric center in pyranosides.
J. Parent (2016)
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