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Osmania University College of Technology
Osmania University College of Technology
TECHNOLOGY
BY
SRAVAN KUMAR.D
M.PHARMACY 1 ST YR 1ST SEM
PHARMACEUTICAL CHEMISTRY
ROLL NO:1008-10-884-008
E1CB ELIMINATION
CONTENTS
INTRODUCTION
TYPES OF ELIMINATION
STEREOCHEMISTRY OF
E1CB
E1,E2,E1CB DIFFERENCES
APPLICATIONS
REFERNCES
Alkyl Halides React with
Nucleophiles and Bases
Alkyl halides are polarized at the carbon-halide bond,
making the carbon electrophilic
Nucleophiles will replace the halide in C-X bonds of
many alkyl halides(reaction as Lewis base)
Nucleophiles that are Brønsted bases produce
elimination
2
11.7 Elimination Reactions of
Alkyl Halides: Zaitsev’s Rule
Elimination is an alternative pathway to substitution
Opposite of addition
Generates an alkene
Can compete with substitution and decrease yield,
especially for SN1 processes
10
11
Mechanisms of Elimination
Reactions
Ingold nomenclature: E – “elimination”
E1: X- leaves first to generate a carbocation
a base abstracts a proton from the carbocation
E2: Concerted transfer of a proton to a base and
departure of leaving group
12
Elimination Reaction: Zaitsev’s Rule
Elimination reactions can take place by different
mechanisms
• E1, E2, and E1cB reactions
– Differ in the timing of C-H and C-H bond breaking
– All three mechanisms occur in laboratory
– E1cB predominates in biological pathways
Elimination Reaction: Zaitsev’s Rule
C hapter 6 94
In reality there is a spectrum of reaction mechanisms!!
“pure” “pure”
E1cb E1
E2
Hofmann Saytzeff
O X
typical situation for E1cb
C C C
H next to C=O (easy to remove)
H X = strong base (difficult to break bond)
E1cb E2 E1 E1 E1 acid
assisted
Syn elimination often occurs and it is associated with poor leaving groups or theabsence of an
anti-beta hydrogen. The bicyclic compound shows syn elimination becauseno anti beta hydrogen
is available because of the geometry of the system. In open chain
compounds, leaving groups such as +NR3 and F show strong tendencies for synelimination
especially in long chain carbon systems
Reactions that produce stabilized carbanions adjacent to poor leaving groups provide
the best evidence for the E1cb process. The elimination of quaternary ammoniums salts,
also called Hoffmann elimination, is believed to follow a carbanion process with syn
elimination and the formation of the least substituted alkene
When reactions show E1cb character they generally produce the least
substitued alkene as the major product. This occurs because carbanion stability is of the
order: primary> secondary > tertiary. In the example below the major product comes from
the carbanion formed at the secondary carbon atom.
Proton-Activating
Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish between Concerted E2
and E1cb Irreversible Mechanisms ... The high values of MethylAF are in agreement with an
irreversible E1cb mechanism (ANDE* + DN) for substrates 5 and 7 and with the high stability of the
intermediate carbanion related to its enamine-type structure. ... These high PAF values are
indicative of an irreversible E1cb mechanism rather than a concerted E2 (ANDEDN) mechanism. ...
Negative Ion Hyperconjugation and Its Relevance to the Mechanism of E1cB Reactions.
An ab Initio Study
Negative Ion Hyperconjugation and Its Relevance to the Mechanism of E1cB Reactions. ... Some
time ago I proposed that E2 and E1cB(irrev) mechanisms could be distinguished by the observation
of a leaving group isotope effect or element effect in the former but not in the latter case. 1 This
argument assumes that there is no weakening of the bond to the leaving group in the rate-
determining proton transfer of the E1cB reaction. ... This is the kind of transition structure one
would expect for a concerted E2 but not for an E1cB mechanism! ...
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism ... Proton-Activating
Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish between Concerted E2
and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-Activating Factors as a
Mechanistic Test To Distinguish between Concerted E2 and E1cb Irreversible Mechanisms
s
The Mechanism of Base-Promoted HF Elimination from 4-Fluoro-4-(4-nitrophenyl)butan-2-one Is
E1cB. ... This new data clearly demonstrates that the elimination proceeds via an E1cB
mechanism. ... These results rule out an E1 mechanism in which the rate-limiting detachment of
the leaving group precedes a fast proton-transfer step but are consistent with a rate-limiting bond
breakage of the proton being transferred in either a concerted E2 or a stepwise E1cB mechanism
Iminium Catalysis
The iminium-activated reaction will be catalytic only if the amine catalyst is released in the final
hydrolysis or elimination step. ... If intermediate 449 is treated with triethylamine and a drying
agent instead of K2CO3, a molecule of water is eliminated by an E1cB mechanism, yielding the
condensation product 450. ...
A synthesis of the ABC framework of dumsin is described. The optically active intermediate 9b,
which is expeditiously assembled from 5-oxobornyl pivalate by the sequential implementation of
an oxy-Cope rearrangement and an intramolecular ene reaction, proved to be suitably
functionalized for ultimate conversion to 5. The synthesis plan relies on two approaches to this
targeted intermediate. In the first, the exocyclic double bond introduced during EtAlCl 2-promoted
closure of aldehyde 10b is cleaved to leave a carbonyl group that is amenable to hydride
reduction and elimination of water. Cleavage of the resulting double bond with ruthenium
tetroxide provided the seco ketoacid. The same advanced intermediate was obtained by initially
positioning the double bond internal to the five-membered ring in advance of transient ring
expansion via diketone formation and intramolecular aldolization. Both of these approaches
bypass the complications arising from the substantial steric congestion prevailing in these
structural networks. The task of covalently positioning an oxygen atom adjacent to the gem-
dimethyl-substituted carbon in 5 was properly realized by oxidative decarboxylation. The
stereochemical assignments to many of the intermediates were confirmed by an X-ray
crystallographic analysis of
In the first, the exocyclic double bond introduced during EtAlCl 2-promoted closure of aldehyde
10b is cleaved to leave a carbonyl group that is amenable to hydride reduction and elimination of
water. ... The assumption was made that the syn elimination envisaged for 37 (Scheme 7) would
not prove problematic in light of the possible operation of the E 1cb mechanistic option. ...
Total Syntheses of Epothilones B and D
Total syntheses of the microtubule stabilizing antitumor drugs epothilone B and D are described,
starting from optically pure (S)-malic acid and methyl (R)-3-hydroxy-2-methylpropionate.
Obviously, anion 21a had undergone an intramolecular proton shift followed by an E1cB
elimination
The final step is the acid-catalyzed elimination of the C1 hydroxyl group catalyzed by His101. ...
Scheme 2. Proposed E1CB Mechanism for the Enzymatic Conversion of 3-Dehydroquinic Acid (1) to
3-Dehydroshikimic Acid (2) Catalyzed by Type II Dehydroquinase Indicating the Residues Involved
in the Catalysis ...
detected in the crude reaction mixture (by 1H NMR analysis) when 10a was allowed to react with
1. ... An efficient one-pot method for bromination−elimination ...
For four albumin concentrations, the observed pseudo-first-order rate constants of chiral inversion
k(R-to-S) and k(S-to-R) as well as those of hydrolysis were estimated by fitting of a two-compartment
kinetic model with elimination from both compartments to the measured concentrations of (R)-
and (S)-thalidomide during incubation of either enantiomer. ... In theory, hydrolysis might also
occur via an E1cb mechanism and a ketene intermediate stemming from the same carbanion
involved in chiral inversion and deuterium exchange.
The pH−rate profiles of 6a−g also differ significantly from those for simple ester hydrolysis, which
occurs via an addition−elimination mechanism and usually exhibits the incursion of specific base
catalyst at ph6-7The
Transformation of Arylmethylamines into α-Aminophosphonic Acids via
Metalated Phosphoramidates: Rearrangement of Partly
Configurationally Stable N-Phosphorylated α-Aminocarbanions
Its formation starts very likely with the generation of imine 19 by elimination (E2 or E1cB) of p-
toluenesulfinate from 6b. ... LDA did not effect elimination of p-toluenesulfinate, but metalation
of the p-tolyl ring ortho to the sulfonyl group
An E1cb pathway for the formation of the α,β-unsaturated α-nitrosulfone has been considered,
but no supporting evidence has been obtained for it. ... The scope of the tandem
nitroaldol−elimination sequence was next investigated by examining a series of aldehydes
. ... 24 Loss of the homoallylic silyl ethers, presumably through E1 cb elimination, was evident in the
1
H NMR spectrum of the crude reaction mixtures. ... The lithiated sulfone was quenched with
PhSSO2Ph,26 and Et3N was introduced into the reaction vessel to scavenge the benzenesulfinic acid
generated in the elimination reaction
A Conformationally Locked Analogue of the Anti-HIV Agent Stavudine.
An Important Correlation between Pseudorotation and Maximum
Amplitude
This important intermediate was to be obtained from the readily accessible 5-(benzyloxymethyl)-
4-(benzyloxy)bicyclo[3.1.0]hexan-2-ol (3),5 following a sequence designed to give the olefin after
elimination of the C4-OH (Scheme 1). ... The optimized yield for this reaction was only 51%,
possibly reflecting the less than ideal geometry (Figure 2C) that forces elimination via a two-step
process (E1cB mechanism
The coupling of 7 with aniline in the presence of ethyl chloroformate and triethylamine 13 produced
the 4,5-unsaturated amide 11 as a result of the base-promoted elimination of acetic acid in
addition to the amide formation.
From these results, an elimination−free radical polymerization mechanism is proposed. ... The
result is consistent with the (E1cb)rev mechanism in which the departure of the leaving group is
rate-limiting.
24
Depending on the structures of the starting sulfoxides, both E1cb and E2 type pathways are
known to give the α-thiocarbocation intermediates from sulfoxides. Design, Synthesis,
and In Vitro Testing of α-Methylacyl-CoA Racemase Inhibitors
We envisaged that elimination of fluoride from the proposed enolate by an E1cB mechanism
within the active site would generate an α,β-unsaturated thioester that may then undergo attack
by an active site base or nucleophile to give the inactivated enzyme. ... The fluorination proved
to be particularly low yielding (20%), a consequence of the propensity for elimination of fluoride,
which could be limited at low temperature
A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of
Aryl N-(Substituted Phenylsulfonyl)carbamates ...
The cyclopropanation of allene itself gives poor results, 40-42 but the addition of dichloro- or
dibromocarbene generated in several ways (base-induced elimination from CHX3 or
trihaloacetate, thermal decomposition of phenyl(trihalomethyl)mercury or
trichloromethyltrifluorosilane) to 1,1-disubstituted allenes afforded MCPs 44 in high yields
(Scheme 10). ... Treatment of bromoalkenes with bases (KOt-Bu) is not as effective as the previous treatments with allyl bromides, producing always mixtures of
elimination products besides ACPs and MCPs. ... The double Michael addition of malonate on trichloronitroethylene followed by double HCl elimination produced a
These results can be interpreted in terms of two competitive processes: the desired SN2
displacement of endo-mesylate 14 by the azide anion and the β-elimination of methanesulfonic
acid from 14 induced by the basic medium (fluoride anion-induced E 1cb elimination) and producing
intermediate alkene 17. ... This is consistent with the intervention of an SN2 displacement process
that is retarded less at lower temperatures than the elimination process (Scheme
3). ...Glutathione-Dependent Metabolism of the Antitumor Agent Sulofenur. Evidence for
the Formation of p-Chlorophenyl Isocyanate as a Reactive Intermediate
Since decomposition of carbamate thioester conjugates in aqueous media is known to take place
primarily via a base-catalyzed elimination E1cb reaction (37), the GSH conjugate, SCPG, can be
expected to be even more unstable in the basic environment of bile than in neutral solution. ...
Most likely, depletion of substrate and product reflects elimination from each conjugate of CPIC,
which undergoes hydrolysis and subsequent decarboxylation. ... However, this low molecular mass
(127 Da) aniline derivative may serve as a useful indicator of metabolic flux through the
isocyanate pathway, although it should be recognized that its excretion into bile would reflect the
aggregate of direct hydrolysis and elimination of the parent diarylsulfonylureas. ...
Generation, Stability, and Reactivity of Small, Multiply Charged Ions in the Gas Phase
For example, the competition of substitution and elimination in the reactions of nucleophiles Y-
with alkyl halides (e.g., RCH2CH2X) according to reactions 6a and 6b formed the subject of
numerous studies. ... This reaction proceeds via an E1cB mechanism which involves a net
cancellation of charges, i.e., an anion and a cation only yield neutral products.
FR901464 is
Facile epoxide opening by β-elimination gave two enones, one of which could undergo
dehydration via its hemiketal to form a furan. ... We speculate that the low yields for these
reactions are due to an intramolecular deprotonation−elimination pathway; the alkoxide
generated after addition to the aldehyde can intramolecularly deprotonate a hydrogen atom at C2
and induce an E1cb reaction
This is followed by the release of H4folate from the ternary complex (step 5, E1CB mechanism)
(13) which generates the exocyclic methylene intermediate (E). ... (ii) The abstraction of the
proton from C5 of dUMP involves E2 elimination of C146 (step 4‘). ...
Effects of Altering the Electronics of 2-Methoxyestradiol on Cell
Proliferation, on Cytotoxicity in Human Cancer Cell Cultures, and on
Tubulin Polymerization
The sulfone resins are then cleaved by β-elimination in the gas phase or in solution by secondary
amines to produce acids and primary, secondary, or tertiary amines. ... In general, cleavage rates
were pseudo first order in substrate and consistent with the accepted E1cB mechanism,17 a
potentially reversible deprotonation followed by an E1 elimination, and were correlated with the
leaving group ability. ...
Kinetics and Mechanism of the Benzenethiolysis of 2,4-Dinitrophenyl
and 2,4,6-Trinitrophenyl Methyl Carbonates and S-(2,4-Dinitrophenyl)
and S-(2,4,6-Trinitrophenyl) Ethyl Thiolcarbonates
Although it is known that ArO- is a better nucleofuge compared to an isobasic Ar‘S-, as judged by
elimination rate constants from the conjugate bases of the corresponding esters (E1cB
mechanism),17 presumably the rate constant k2 (DNPO- expulsion from 2) is not greater than k-1
(isobasic Ar‘S- expulsion from 2). ...
Moreover, the subsequent elimination (E2 or E1cB) from the betain intermediate (nitrogen and
phosphane betain) should also have some differences (Figure 2, C and D). ...
Regioselectivity and the Nature of the Reaction Mechanism in
Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted
Benzenesulfonates with Primary Amines
In fact, an upward curvature in the Hammett plots has often been reported for nucleophilic
substitution reactions of the benzylic system or those of various carboxylic esters (e.g.,
substituted phenyl esters of 4-nitrophenylacetic acid) in which a change in reaction mechanism
occurs from SN1 to SN2 for the former case and from a bimolecular reaction (either one step or a
stepwise addition−elimination mechanism) to an E1cB mechanism for the latter
case. ...Elucidation
of the Electron Transfer Reduction Mechanism of
Anthracene Endoperoxides
elimination mechanism and formation of PPA. ... According to the mechanism in Scheme 2, protonation of the alkoxide anion portion is required for elimination of
Having a good leaving group in the β-position to the anionic center a glycosyl anion may undergo
an E1cB elimination to give glycals VIII. ... On the other hand, elimination of an oxide or hydride,
which is known with simple carbanions, 43 has rarely been observed with glycosyl anions,
presumably because of the slight stabilizing effect of the ring oxygen. ... On the basis of
deuteration experiments, it was suggested that the reaction proceeded through an E2 rather than
the expected E1cB mechanism. ...
The trans-diequatorial arrangement would permit a concerted elimination of the cofactor and H-
C5 from dUMP, and would orient the transferred methylene group in a manner consistent with the
stereospecificity of hydride transfer (22, 23). ... In particular, they show that the stereospecificity
of hydride transfer can be ascribed to a two-step (E1CB) elimination of first, dUMP H-C5 and then
the cofactor from intermediate II, a mechanism which does not require conversion of the trans-
diaxial orientation of the catalytic sulfhydryl and methylene bridge to a trans-diequatorial
arrangement. ...
Biodegradable Hydrogels for Time-Controlled Release of Tethered
Peptides or Proteins
To demonstrate the elimination of attached PEG chains, 100 μL of this solution were diluted with
900 μL of 50 mM borate buffer, pH 9.0, and incubated for 24 h at 50 °C. ... These carbamates
hydrolyze in neutral and basic solutions by an E1cB elimination reaction involving the
intermediate formation of an unstable isocyanate.
Reduction of Oxamyl and Related Pesticides by FeII: Influence of Organic Ligands and
Natural Organic Matter
Pseudo-first-order rate constants for the reduction (kred, h-1) and E1cb elimination (kelim, h-1) of
oxamyl and methomyl were determined for each batch reaction using data for both parent
compound disappearance and reaction product appearance according to a procedure outlined
previously (25) (details provided in the Supporting Information). ... In addition, the organic ligands
have no effect on the rates of a parallel E1cb elimination reaction (discussed in detail in ref 24).
Extended ElcB mechanism for ester hydrolysis: allylic substitution via carbanion in
ester hydrolysis
Off and on the enzyme, scytalone undergoes E1cb-like dehydration reactions that are
differentiated by the greater commitment to product formation (elimination) following
enolization in the enzyme-catalyzed reaction (
Using Pd-based catalysts, the low yields observed in the coupling of certain substrates have been
attributed to the slow rate of C−O reductive elimination relative to β-hydride elimination from
the LnPdII(Ar)(alkoxide) intermediate. ... The use of KOPh as an additive is significant in
determining the outcome of the process since in the absence of this base, the initial product of
oxidative insertion undergoes direct reaction with the ester carbonyl to yield a 2,3-
dihydroquinolin-4-one. The researchers reasoned that addition of a basic species would serve to
enolize the ester, but the potential for elimination of the aniline fragment via an E1cB
mechanism steered them from the use of stronger bases such as KOtBu. Depending on the
substrate, indolines can sometimes be isolated from this reaction, but in most cases these convert
directly to indoles under the reaction conditions.
This topology is consistent with other β-elimination enzymes (37). ... This suggests an E1cB
mechanism rather than an E2 mechanism for this elimination reaction, which occurs with trans
stereochemistry. ...
In fact, carbinolamides exhibit a form of reactivity in water wherein the amide portion of their
structure acts as a leaving group in what could be formally described as an elimination reaction
(see Scheme 1). ... Previous studies investigating (E1cB)R reactions where an amidate acted as a leaving group were shown to undergo relatively slow rate
determining departure of N-methylacetamidate in ethanol in the presence of ethoxide (k = 4.6 × 10-6 s-1 for PhSO CH CH NHCOCH in EtOH/NaOEt at 25 °C). ...
obsd 2 2 2 3
These studies clearly show that amides are capable of acting as leaving groups in elimination reaction supporting (E1cB) studies performed by Stirling. ...
R
Phosphonylpyrazoles from Bestmann−Ohira Reagent and Nitroalkenes:
Synthesis and Dynamic NMR Studies
According to the proposed mechanism,(30) the nucleophilic base mediated acyl cleavage of BOR 2
followed by cycloaddition of the resulting diazomethylphosphonate anion with nitroalkene 1a
provides initial cycloadduct which undergoes elimination to afford phosphonylpyrazole 3a. ... This
was explained primarily in terms of the elimination of HBr by an E2 mechanism and HNO2 by an
E1cB mechanism from the initial cycloadducts. ... However, in the case of 8b and 8d, a
competing E1cB mechanism is also operative which leads to the formation of a mixture of 9 and
10. ...
Compound 1 is chemically labile in alkaline solution, leading to epimerization and degradation via
the E1cB mechanism to give cytosine. ... However, interestingly, the formation of guanine and 1,4-anhydro-2-C-cyano-2-deoxy-D-erythro-pent-
l-enitol (18, glycal), which were β-elimination products of 3, was more suppressed than that of 1.
The alkaline hydrolysis of the title esters, possessing three conjugated units between the internal
nucleophile (the hydroxyl group) and the reaction center, follows an E1cB mechanism involving
the participation of an extra extended p-oxo azoketene ... ... The alkaline hydrolysis of title
esters possessing acidic leaving groups follows an E1cB mechanism involving the participation of
an extra extended p-oxo ketene intermediate. ... Reactivity comparison, Arrhenius parameters,
and trapping of the above-depicted unsaturated intermediate strongly suggest that the alkaline
hydrolysis of the title ester follows a mechanism of the E1cB type.
triethylamine12) were unsuccessful due to partial isomerization of the double bond. ... 20
Thus, it would appear most likely that the
elimination takes place via either an E1cb mechanism or by an E2 mechanism in which the
isomeric nitro acetates can interconvert (Scheme 17). ...
Unusual Mechanism for an Aminomutase Rearrangement: Retention of
Configuration at the Migration Termini
The lyases share a characteristic active site motif, alanine−serine−glycine (ASG), that
autocatalytically rearranges to form a functional 3,5-dihydro-5-methylidene-4H-imidazol-4-one
(MIO) prosthesis acting as a Lewis acid to promote the elimination of NH3 and H+ from the
arylalanine substrate (8). ... The PAL-mediated elimination process begins with removal of the
pro-3S hydrogen likely by the 137His residue of PAL from Rhodosporidium toruloides (17), followed
by E1cb-type displacement of ammonia from the substrate to form trans-cinnamate (15, 17) (Figure
2B). ... Alternatively, the MIO is attacked by the amino group to facilitate Hoffmann-type
elimination of the NH3/H+ (amine comple
Finally, the proton transfer generates intermediate 10, followed by elimination of Bu3P to
afford the desired product 3 or 4. ... Then, the trans elimination (E1cb type) of DMAP from
14 affords product 5 with E configuration, and regenerates DMAP. ...
Positional Ordering of Reacting Groups Contributes Significantly to the
Efficiency of Proton Transfer at an Antibody Active Site
promoted E2 elimination of
substituted benzisoxazoles (Scheme 1),4,5 also known as the Kemp elimination. ... 7
Mechanistic studies suggest either an E1cb or an
H50
E2 elimination mechanism, in which Glu , the same functional group utilized by 34E4, serves as
the general base
Specifically, the sequence of elimination events, glycosidic bond cleavage and rearomatization of
the estrogen A ring, was explored. ... Reverse Michael addition between pyridine nucleophiles and
Michael acceptors has been shown to proceed via an E1cB mechanism, where proton removal is
the rate-limiting step (37). ...
Following the language used in β-elimination reactions, to which these fragmentation have been
correctly assimilated,8 these transition states might be indicated as E1cb-like. ... In conclusion,
stereoelectronic effects seem to play a very minor role in the fragmentation of 2-phenylsulfanyl
alcohol radical cations, probably due to a process that, as said before, is shifted to the E1cb side
of the mechanistic spectrum.
Evidence for an irreversible E1cB mechanism for base-induced sulfine formation from methyl
diarylmethanesulfinates ...
These intermediates are formed by an anti elimination of UDP from UDP-GlcNAc and a syn
elimination of UDP from UDP-ManNAc. ... The first is an E1cb mechanism in which an initial
deprotonation event generates a carbanionic intermediate prior to expulsion of the leaving group.
derivatives involving the intermediacy of ketenes is well documented. ... 17 Because the presence of electron-withdrawing groups is known to substantially facilitate
elimination reactions, some carboxylic acid derivatives possessing relatively poor leaving groups can also generate ketenes with the elimination mechanism ranging from
E2 to E1cB ... 18
Consequently, aminolysis of activated esters including acetoacetyl and malonyl
coenzyme A derivatives proceed through a E1cB mechanism.
Influence of steric effects upon the rate constants for competing BAC2 and E1cB ester
hydrolyses
Influence of steric effects upon the rate constants for competing BAC2 and E1cB ester
hydrolyses ...
Associative and Dissociative Pathways in the Alkaline Hydrolysis of Aryl 2-
Hydroxycinnamates
The alkaline hydrolysis of title esters possessing acidic leaving groups follows an E1cB mechanism
involving the participation of an extra extended p-oxo ketene intermediate. ... Reactivity
comparison, Arrhenius parameters, and trapping of the above-depicted unsaturated intermediate
strongly suggest that the alkaline hydrolysis of the title ester follows a mechanism of the E1cB
type. ... To gain knowledge on the role played by the nature of the bridge interposed between
hydroxyl and carbonyl groups in esters of the title type, in principle able to hydrolyze through
dissociative pathways via the conjugate base of the substrate (E1cB ... ...
derivatives involving the intermediacy of ketenes is well documented. ... 17 Because the presence of electron-withdrawing groups is known to substantially facilitate
elimination reactions, some carboxylic acid derivatives possessing relatively poor leaving groups can also generate ketenes with the elimination mechanism ranging from
E2 to E1cB ... 18
Consequently, aminolysis of activated esters including acetoacetyl and malonyl
coenzyme A derivatives proceed through a E1cB mechanism
The synthesis involves a Claisen-type condensation in which the elimination was unexpectedly
promoted by an excess of the ester. ... The type of elimination (E1, E2, or E1cB) by which the
reaction takes place has not been determined since such an investigation was beyond the scope of
this work.
Biomimetic Transannular Oxa-Conjugate Addition Approach to the 2,6-
Disubstituted Dihydropyran of Laulimalide Yields an Unprecedented
Transannular Oxetane
Removal of Acyl Protective Groups from Glycopeptides: Base Does Not Epimerize Peptide
Stereocenters, and β-Elimination Is Slow ... O-Linked glycosides of serine and threonine have
been suggested to undergo E1cB elimination in aqueous sodium hydroxide with an amino acid
enolate ion as an intermediate.
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism
Large, inverse solvent isotope effects: a simple test for the E1cB mechanism ... Catalysis of the β-
Elimination of HF from Isomeric 2-Fluoroethylpyridines and 1-Methyl-2-fluoroethylpyridinium
Salts. ...
The key step of the sequence involves addition and elimination of an enolic lactam in a single
step and 70% yield, employing an organocuprate reagent. ... The elimination of the acetate group
of compound 7 leading to E-Boc-pulchellalactam 8 with high E selectivity proceeded presumably
via the E1cB mechanism42-46 with the help of a steric factor from the N-Boc moiety. ... We assume
that allylic deprotonation of compound 4 and condensation with aldehyde led to Z-
pulchellalactam 1 also through an E1cB mechanism42-46 via tert-butoxycarbonyl group (Boc)
migration (Scheme 3). ...
13, 15) As a means to introduce desired substituents at the 3 and 6 positions of the 2,5-
diketopiperazines, a majority of synthetic studies have been devoted to the
elimination−nucleophilic attack of compounds A in the presence of nucleophiles, often under
acidic conditions, to form B (Scheme 1a). ... (26) One plausible explanation for the cis selectivity
is an E1cb pathway through the transition state 8β. ...
NaOH-Catalyzed Thiolysis of α,β-Epoxyketones in Water. A Key Step in
the Synthesis of Target Molecules Starting from α,β-Unsaturated
Ketones
benzoylcytosine failed to give our desired protected nucleosides 27‘, but the regioisomer 27 was obtained in 47% yield (two steps) along with β-elimination product 28 in
Among them, there would be two betaine intermediates B and C that are stabilized through
hydrogen-bonding between the amidate ion and the phenolic OH. On taking the anti-periplanar
arrangement13 of the ammonium portion and the α-hydrogen of the ester group in the subsequent
E2 or E1cb reaction (see Newman projection D), intermediate C suffers from more severe steric
interaction than intermediate B as depicted in Scheme 4. Thus, the difference in the reaction rate
of the elimination step of B and C would result in (S)-enriched enantioselectivity through
equilibration
In principle, other mechanisms could not be ruled out, for example, the direct formation of a
ketene from a with a E1cb elimination and its subsequent reaction with a molecule of acid and
one of isocyanide, in a way similar to that reported by Ugi, although the absence of a base
catalysis makes this hypothesis less likely. ...
Multicomponent Reaction Discovery: Three-Component Synthesis of
Spirooxindoles
The product of E1CB elimination of 27 (an isatylidene) cannot be ruled out as a reaction
intermediate. ...
The role of Et3N is most likely to promote elimination and liberation of the phosphine catalyst via
either E2 or E1cb mechanisms. ...
e had speculated that 2 arose from 1 via a ring-opening reaction involving an elimination process.
... The stereochemical outcome of the base/TMSCl-initiated ring-opening reaction of 1 and 3 can
be rationalized as occurring through an E1cB mechanism, as shown in Scheme 3.
One-Pot Organocatalytic Domino Michael-Aldol and Intramolecular S N2
Reactions. Asymmetric Synthesis of Highly Functionalized
Epoxycyclohexanone Derivatives
The organocatalytic reaction is based on the full stereochemical control of first a Michael
reaction, followed by an aldol reaction, and finally, depending on the product of choice, a S N2 or
an E1cB reaction. ... Scheme 4. One-Pot Domino Organocatalytic Michael-Aldol and Elimination
Reactiona
-9
One of the most popular versions of this reaction utilizes enamines 2 as dienophiles in an
inverse-electron-demand Diels−Alder reaction, followed by in situ loss of nitrogen from 3 and
subsequent elimination/aromatization (Scheme 1). ... This could allow, for instance, either an E1cb mechanism (if the anion was
sufficiently stable) or epimerization of this carbon center, leading to an anti-arrangement of proton and adjacent leaving group and hence a facile E2 elimination. ...
Thus, zwitterion 4‘ could facilitate elimination to the corresponding pyridine (by allowing an E1cb mechanism or epimerizing adjacent to the amine leaving group).
followed by base treatment (eq 1).2 Later, the reaction was successfully expanded to the 1-(alkoxycarbonyl)methyl-2-methylpyridinium system leading to 2,3-dihydro-2-
indolizinones.5 A mechanism proposed for the reaction was that by the base-treatment of the pyridinium salts, the corresponding ylide was formed as an reactive
intermediate and indolizines were produced via an intramolecular nucleophilic attack of the active methylene to the carbonyl group followed by elimination of water (or
alcohol). ... For alcoholysis (R ≠ H), cyclization to indolizinone F proceeds through ketene intermediate E, which is formed from C by the elimination of R1 presumably via
Reduction of the Pesticides Oxamyl and Methomyl by FeII: Effect of pH and Inorganic
Ligands
Treatment of nonstabilized β-hydroxy phosphonic acid mono methyl esters with diisopropyl
carbodiimide at ambient temperature leads to clean stereospecific elimination. ... In the
Wadsworth−Emmons reaction,6 the reversible formation of the pentavalent phosphorus species 15
is thought to precede collapse to the stabilized anion 16, and E1cb elimination leads to release of
phosphate and the coupled enone product 17 (Scheme 3).
The elimination
pathway is not consistent with the E2 mechanism owing to stereoelectronic effects. ... It is known
that the E1cB mechanism would most likely be found with substrates containing acidic protons
and poor leaving groups
The 2,5-elimination of pyruvate from SEPHCHC by MenH can occur by simultaneous proton
abstraction and pyruvate dissociation in a concerted E2 elimination or through a dienolate
intermediate in a two-step E1cb ... The one-step elimination is not favored in view of the well-
established notion that base-induced β-eliminations involving breakage of a C−H bond at an α-
position to a carbonyl group proceed by an E1cb mechanism rather than a concerted mechanism
(54). ... In comparison to 3-flourocyclohexene, SEPHCHC has a much more acidic proton in the
elimination due to the 2-succinyl group and a poorer leaving group (pyruvyl enolate) than
fluoride, both of which strongly favor an E1cb mechanism (54-56). ...
6
Expectations that this E1cb irreversible elimination ... It was found that incubation of a D2O
solution of 4 and 5 for a day at pD = 9.4 resulted in significant elimination of phosphate from 5
even before 4 had undergone significant enolization (as evidenced by the lack of exchange of the
CH2 (and CH) protons of 4 for deuterons).
This would be possible if carboxylic derivatives of type 5 possess a relatively weak X-CO bond that
would provide a sizable equilibrium concentration of ketene of type 2, and there is a possibility
for fast elimination of HX in the absence of basic catalysts (i.e., tertiary amines) that can produce
undesirable zwitter-ionic adducts. ... The only relevant, similar examples involve generation of ethyl ketenes from N-acylbenzotriazoles by
thermolysis17 or treatment with NaH.18 These harsh conditions are understandable, since the low basicity of imidazole is not sufficient for producing ketenes from N-
acylimidazoles through E1cb elimination reaction. ... Most probably, the lack of reactivity of alkylsulfinylacetic acids is due to the lower acidity21 of the α protons that
precludes E1cb elimination of imidazole in the corresponding N-acylimidazoles and formation of ketenes of
We hypothesized that the instability of 9 and 10 may be caused by their intramolecular E1cB
elimination, in which the amine group may play dual roles as shown in Scheme 5 (by using 10 as a
model). ... Thus, the amide-protected(9) (as a weak base) or α,α-disubstituted(13) (without α-
protons) aldehydes were successfully prepared in literature because they could not carry out an
intramolecular E1cB elimination. ... aA retro-Micheal addition by an intramolecular E1cB
elimination ...
s
The well-known Wittig reaction provides access to C═C bonds with higher efficiency and better regio-
and stereoselectivities over the classical elimination reactions (E1, E2, E1cB). ... Finally, reductive
elimination affords the decarbonylative addition product and CO and regenerates the active ruthenium complex A
Probing the Catalytic Mechanism of S-Ribosylhomocysteinase (LuxS)
with Catalytic Intermediates and Substrate Analogues
Since [3-F]SRH reacted much faster than [3-Br]SRH, the elimination reaction must occur
through the E1cb mechanism (i.e., rate-limiting abstraction of the C2 proton to form a
carbanion intermediate first, followed by the fast release of halide ion). ... [3-F]SRH and
[3-Br]SRH, while disappointing as suicide inhibitors, provide alternative substrates to
examine the function of active-site residues during the first catalytic step, since the E1cb
elimination reaction involves initial deprotonation at the C2 position, which closely
mimics the deprotonation event in the first catalytic step. ... Substrate analogues [3-F]SRH
and [3-Br]SRH act as time-dependent inhibitors of LuxS, due to enzyme catalyzed
elimination of the halide ions via an E1cb mechanism. ...
(8) In this paper, we present a simple, general, palladium-free method for the synthesis of
highly substituted dibenzopyranones using a Diels−Alder reaction between 4-
cyanocoumarins and 1-oxygenated dienes followed by elimination−aromatization with
potassium tert-butoxide. ... Further support for the E1cb mechanism was obtained from
the regioisomeric Diels−Alder adduct 17, prepared in good yield from the reaction of 3-
cyanocoumarin and the 1-silyloxybutadiene 7
Synthesis of Substituted Chromanones: An Organocatalytic Aldol/oxa-
Michael Reaction
) Thermolysis of β-ketoesters 4 leads to the loss of ROH via concerted elimination. ...
Either of the resulting cationic intermediates 17 and 18, upon proton loss, would give the
zwitterion 19, which could collapse directly to acetylketene (20) [Douglas and co-workers
have shown(14) that E1cb elimination from the anion of thioacetoacetates (acetoacetyl
CoA) is facile
Protection of the diol as the bismethyl ether was followed by oxidation of the sulfide to the
sulfone 9b and elimination of the OMe group to yield vinyl sulfone 10 in 78% overall yield (Scheme
1). ... Anion 22b is perfectly set for an E1cb elimination of potassium phenylsulfinate to afford
the desired vinyl phosphonate 21. ... This is presumably because the initially formed alpha-
sulfonyl anion suffers immediate E1cb elimination of the −OH group and gives a new vinyl sulfone.
...
Protection of the diol as the bismethyl ether was followed by oxidation of the sulfide to the
sulfone 9b and elimination of the OMe group to yield vinyl sulfone 10 in 78% overall yield (Scheme
1). ... Anion 22b is perfectly set for an E1cb elimination of potassium phenylsulfinate to afford
the desired vinyl phosphonate 21. ... This is presumably because the initially formed alpha-
sulfonyl anion suffers immediate E1cb elimination of the −OH group and gives a new vinyl sulfone.
The data obtained are consistent with a mechanism for conversion of S-Fmoc to S-Fm via
the expected elimination/addition reaction pathway shown in Scheme 3. ... The
mechanism for β-elimination in the fulvene system has been postulated to lie on the
borderline between E1cb ... When the mechanism is E1cb (presumably as it is for
nitrogen), the rate of reaction becomes dependent on removal of the Fmoc β-hydrogen. ...
Stereocontrolled Synthesis of (−)-Macrolactin A
When the alcohol is protected as its methyl or silyl ether, β-elimination results, thus
lowering significantly the yield of the desired adduct. ... Unfortunately, the
stereoselectivity of the elimination in this case was only 2:1, E/Z. ... We postulated that
the improvement in stereoselectivity may be attributed to the greater propensity of the
benzoyloxy group toward elimination (Ka = 6.46 × 10-5 vs acetic acid Ka = 1.76 × 10-5). ...
Identity and distribution of products formed during the acidic hydrolysis of compounds 1a−h are
consistent with the mechanistic pathway shown in Scheme 1 in which two competitive E1cB
reactions (kCO and kSO2) are involved. ... (7) The small values of kH2O/kD2O observed for kCO in 1.0 M
LCl are not incompatible with the elimination pathway c (eq 7
We are looking for probes for delineating the mechanism of bimolecular nucleophilic vinylic
substitution proceeding by an initial nucleophilic attack on the double bond (the
“addition−elimination” route).1 With mildly activated systems the stronger evidence for a
multistep route via an intermediate carbanion (eq 1) (i.e., A being an intermediate and not a
transition state) is the element effect (the relative rates k when X = F, Cl, Br, e.g., kBr/kCl),2 which
Olefin 7 had been prepared previously by Martin sulfurane dehydration (70%) 7 where other
more conventional elimination techniques proved unsuccessful. ... Undoubtedly, this reaction can be
considered of the E1cB type, owing to the presence of the cyclohexanone carbonyl.
These pyrazoles are formed in one pot via spontaneous elimination of the nitro group. ...
Protonation of 7 followed by base-assisted elimination of HNO2 (path a, E1cB) or
elimination of the NO2 group followed by intramolecular proton transfer (path b) would
furnish phosphonylpyrazole 5
A Theoretical Study of the Chorismate Synthase Reaction
3-5
Of the various possibilities, a concerted E2 or nonconcerted E1cb elimination involving
deprotonation at C6 would likely require a strong base. ... To investigate the E1cb
process, deprotonation at C6 was modeled using DHCCP, and the structure of the resulting
anion was optimized (Figure 2). ... Consistent with that finding, the enzyme-catalyzed
elimination of (6R)-[6-2H]-EPSP displayed a small kinetic isotope effect of 1.13, ...
Theoretical Studies of Eliminations. 6. The Regiochemistry and
Stereochemistry of the Gas-Phase Reactions of 3-Halocyclohexenes
with Fluoride. An ab Initio Study
The two modes of substitution (SN2 and SN2‘) have similar barriers, but are much less
favorable than elimination. ... In previous computational work by Nibbering and co-
workers,10 E1cb intermediates were identified in the reactions of hydroxide and fluoride
with 2-butenyl methyl ether, and it was determined that these intermediates are formed
via barrierless proton transfers
1,2
Recently we reported on the stereoselective formation and elimination of β-
bromosilanes in Lewis acid promoted atom transfer additions to branched allylsilanes. ... This
result can be rationalized by an E1cb mechanism11 for the TBAF-induced elimination from 4d and 4e, a conclusion consistent with observations reported by
Fleming.10 We conclude that the results from all of the transformations are consistent; threo is the major product formed in every case. ... The TBAF
elimination results for substrates 6d and 6e suggest an E1cb elimination mechanism, a result that is consistent with the elimination reaction of thiopyridyls
4d and 4e
Elimination Reactions of (E)- and (Z)-Benzaldehyde O-Pivaloyloximes. ... Since the elimination reactions exhibit second-order kinetics and substantial k /k
H D
values, all but E2 and (E1cb ... 4
The (E1cb) mechanism requires the formation of a carbanionic
irr
Soc., Perkin Trans. 2 2000, 453), PAF = 1.5 × 106 and is in agreement with an E1cb
irreversible mechanism (AxhDE* + DN) (Guthrie, R. D.; Jencks, W. P. Acc. Chem. ... This
proton activation can be accounted for by an E1cb mechanism and by the high stability of
the intermediate formed from the protonated substrate NH+ (Scheme 1). ... It was
previously16 shown that eq 2 reduces to = + , owing to the operating
(E1cb)I mechanism, and the values determined are as follows: = 2.54 × 10-6 s-1
(isomer 1) and = 8.75 × 10-7 s-1 (isomer 2), = 241 M-1 s-1 (isomer 1), and = 290
M-1 s-1 (isomer 2). ...
Kinetic and product studies are consistent with the following: (a) the reaction of
tresylates with water is the normal sulfonic ester hydrolysis and (b) reaction with
hydroxide is an (E1cB)rev process with loss of HF to yield the alkyl 2,2
difluoroethenesulfonate, ROSO2CH CF2, which rapidly yields the observed products. ... It
would appear that the reaction of water (kw term) is exclusively the conventional solvolysis
usual with sulfonic esters, whereas the reaction of hydroxide anion is clearly consistent
with the reversible E1cB reaction shown below. ... A reversible E1cB process is specific
base catalyzed and is therefore not expected to show any acceleration with added amines,
provided they act only as bases and not as nucleophiles. ...
Novel Syn Intramolecular Pathway in Base-Catalyzed 1,2-
Elimination Reactions of β-Acetoxy Esters
The more acidic thioester substrates do not produce an increased amount of syn
stereoselectivity even though their elimination reactions are at the E1cb interface. ... The
research began by a study of the elimination of acetic acid from S-tert-butyl (2R*,3R*)-3-
acetoxy-2-2H1-butanethioate (5) using KOH in 3:1 v/v EtOH/H2O, producing S-tert-butyl (E)-
2-butenethioate (6), Figure 1.5 A previous mechanistic study of the elimination reaction of
S-tert-butyl 3-acetoxybutanethioate (7) had concluded that the reaction was either E2 or
E1cbirrev. ... 2,3,9,10 Thus, electron-withdrawing substituents and poor leaving groups that
produce transition states with more E1cb character may favor syn elimination
Nucleophilicity vs Basicity in the Reaction of Sodium tert-
Butoxide with β-Stannyl Ketones
Stereochemical results suggest that the elimination reactions proceed through an (E1cB)R
mechanism. ... All these observations provide strong evidence for an (E1cB)R mechanism
initiated by proton abstraction by the tert-butoxide ion, as represented in Scheme 2. ...
The E1cB mechanism is also supported by the effect of organotin moieties attached to C-3
and of substituents attached to C-2 on the elimination/substitution rat
The Alkaline Hydrolysis of Aryl (2E)-3-(4‘-
Hydroxyphenylazo)propenoates. A Kinetic Study
The
alkaline hydrolysis of the title esters, possessing three conjugated π units between the
internal nucleophile (the hydroxyl group) and the reaction center, follows an E1cB
mechanism involving the participation of an “extra extended” p-oxo azoketene type
intermediate. ... We have been able to demonstrate that the E1cB ... In the simplest case
we investigated, the hydrolysis of aryl 4-hydroxybenzoates, 2 the π-system was an aromatic
ring and we showed that esters having leaving groups with pKa values lower than about 6.5
hydrolyze through the E1cB mechanism with the participation of the unprecedented p-oxo
ketene intermediate 1.
Mechanism of Alkaline Hydrolysis of Some HO-π-COOAr Acyl
Derivatives
To gain
knowledge on the role played by the nature of the bridge interposed between hydroxyl and
carbonyl groups in esters of the title type, in principle able to hydrolyze through
dissociative pathways via the conjugate base of the substrate (E1cB mechanism), we have
studied the alkaline hydrolyses of 2,4-dinitrophenyl esters in which the π-system is a
biphenyl, azobenzene, benzylideneaniline, or stilbene skeleton. ... We have been
interested in the dissociative (E1cB ... We have previously found1 that the hydrolyses of
aryl 4-hydroxybenzoates in moderately to strongly alkaline aqueous solution follow the
usual associative route (BAc2) when the esters possess leaving groups having pKa higher than
about 6.5, whereas esters having leaving groups with lower pKa hydrolyze through the E1cB
mechanism with the participation of the unprecedented p-oxo ketene intermediate (1
Mechanisms of Acid−Base Catalysis of β-Elimination Reactions in
Systems Activated by a Pyridine Ring
The results of a kinetic study of acid−base catalysis and H/D exchange are consistent with
NH+, the protonated substrate, as the species that undergoes carbon deprotonation with an
E1cb mechanism. ... In previous studies2-5 of systems activated by a nitrophenyl group, the
mechanism of base-induced β-elimination reactions has been shown to be E1cb (ΑxhDH +
DN)6 with the intermediate carbanion formed with different degrees of reversibility
depending on the structure of the substrate. ... H/D exchange experiments showed the
incorporation of deuterium at the β-carbon during the elimination reaction in D2O, in
acetohydroxamate/acetohydroxamic acid buffer, at 50 °C and μ = 1 M KCl, in agreement
with a stepwise reversible mechanism, (E1cb)R(AxhDH + DN*).6 Further support for the
proposed mechanism has come from studies of the solvent kinetic isotope effect. ...
The mechanism involves initial elimination of hydrogen fluoride by an E1cB mechanism to afford
an electrophilic quinone methide- or azafulvene-type intermediate that reacts with secondary
amines under aqueous conditions to afford the tertiary amide in good yield (up to 99%). ... The
mechanism involves initial elimination of HF (via an E1cB mechanism) to give a key electrophilic
quinone methide intermediate, which can be attacked by a range of nucleophiles, such as
hydroxide. ... This lower reactivity may be attributed to the lower acidity of the aniline 4b
compared to the phenol 4a, thus leading to a reduced rate for the initial E1cB elimination of HF.
Aliphatic amines gave good yields of the desired tertiary amides (Table 1, entries 20 and 21).
An Unprecedented Concerted Pathway in the Alkaline Hydrolysis of S-
Aryl Thioesters
Instead, the stepwise E1 and new E1cb mechanisms are suggested to occur and may compete with
each other in the electronic ground state. ... As to the proposed E2-type β-elimination mechanism
for EosFP,(14) after many trials, the concerted E2-type transition state involving the simultaneous
Cα−N bond cleavage and deprotonation by Glu212 could not be found for Kaede (and possible for
EosFP), but the optimization all led to the E1 or E1cb (see below) pathway. ... E1cb Pathway
The alkaline hydrolysis of title esters possessing acidic leaving groups follows an E1cB mechanism
involving the participation of an “extra extended” p-oxo ketene intermediate. ... Break in the
Brønsted plot of the apparent second-order rate constants versus the pKa of the leaving group
suggests that the reaction mechanism changes from E1cB to BAc2 for esters having pKa higher than
about 6. ... In the course of our studies on acyl transfer reactions we have at first provided
evidence that alkaline hydrolysis of aryl esters of 4-hydroxybenzoic acid occurs through either
associative (BAc2) or dissociative (E1cB, via intermediate 1) mechanisms, depending on the
basicity of the leaving group
Carboxylate-Induced Degradation of Poly(3-hydroxybutyrate)s
As the leaving group is made poorer (X = H, OCH3, and Cl), E2 transition state becomes more
skewed toward the proton transfer, as revealed by the increase in Brönsted β to 0.5−0.64, and the
E1cb ... The changes in the k1 and k-1/k2 values with the reactant structure variation provide
additional support for the competing E1cb mechanism. ... Extensive studies of ketene-forming
elimination reactions have revealed mechanistic diversity in the E2 and E1cb
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of
Base-Promoted .beta.-Elimination Reactions from N-[2-(p-
Nitrophenyl)ethyl]alkylammonium Ions
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of Base-
Promoted .beta.-Elimination Reactions from N-[2-(p-Nitrophenyl)ethyl]alkylammonium Ions ...
Proton-Activating Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish
between Concerted E2 and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-
Activating Factors as a Mechanistic Test To Distinguish between Concerted E2 and E1cb
Irreversible Mechanisms
A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of
Aryl N-(Substituted Phenylsulfonyl)carbamates
Evidence for an irreversible E1cB mechanism for base-induced sulfine formation from methyl
diarylmethanesulfinates ...
Top of Form
Equilibration of N-(2-cyanoethyl)pyridinium cations with substituted pyridines and
acrylonitrile. A change in rate-determining step in an E1cb reaction
Evidence for an irreversible E1cB mechanism for base-induced sulfine formation from methyl
diarylmethanesulfinates ...
A General Acid-Catalyzed Anion Breakdown Associated with an E1cB Reaction in the Hydrolysis of
Aryl N-(Substituted Phenylsulfonyl)carbamates ...
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of
Base-Promoted .beta.-Elimination Reactions from N-[2-(p-
Nitrophenyl)ethyl]alkylammonium Ions
Study on the Effect of the Structure of the Leaving Group in the E1cb Mechanism of Base-
Promoted .beta.-Elimination Reactions from N-[2-(p-Nitrophenyl)ethyl]alkylammonium Ions ...
Proton-Activating Factors and Methyl-Activating Factors as a Mechanistic Test To Distinguish
between Concerted E2 and E1cb Irreversible Mechanisms ... Proton-Activating Factors and Methyl-
Activating Factors as a Mechanistic Test To Distinguish between Concerted E2 and E1cb
Irreversible Mechanisms ...
VBSCF Calculations on the Bimolecular (E2) Elimination Reaction. The Nature of the
Transition State
Valence bond state correlation diagrams (VBSCD) show that a simple proton transfer such as that
in the E1cB irreversible reaction is predicted to have a lower barrier than a synchronous
concerted (E2) reaction. ... They found that reactions of a number of 2-arylethyl and 2-cyanoethyl
derivatives gave transition states near the upper left corner of the figure, in some cases into
stepwise E1cB territory. ... (15) Figure 3 is such a diagram for an E1cB reaction with the first step
rate determining. ...
Borderline between E1cB and E2 mechanisms. ... Ab Initio Molecular Dynamics Simulations of
Elimination Reactions in Water Solution: Exploring the Borderline Region between the E1cb and
E2 Reaction Mechanisms ... Ab Initio Molecular Dynamics Simulations of Elimination Reactions in
Water Solution: Exploring the Borderline Region between the E1cb and E2 Reaction
Mechanisms ...
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