Effect of Anchimeric

Assistance in the Reaction

of Triphenylphosphine
with ,-Unsaturated
Carboxylic Acids
ALEXEY V. SALIN, ALBERT R. FATKHUTDINOV, ANTON V. ILIN, VLADIMIR I. GALKIN
A. Butlerov Institute of Chemistry, Kazan Federal University, Kazan 420008, Russia

Received 8 July 2013; revised 9 September 2013; accepted 24 November 2013

DOI 10.1002/kin.20842
Published online 2 January 2014 in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: Quaternization of triphenylphosphine with maleic and cis-aconitic acids is strongly

accelerated by participation of the cis-carboxyl group in stabilization of the phosphonium
zwitterion intermediate by intramolecular hydrogen bonding, in spite of steric hindrance by
the acids reaction center. A similar effect for trans-isomeric acids is not observed, which can
be rationalized on the basis of spatial structures of the generated zwitterions, implying an
electrostatic interaction between the phosphonium center and carbonyl oxygen atom. The
effect of anchimeric assistance decreases when the intramolecular hydrogen bonding disfavors
attack of the phosphine on the sterically less hindered carbon atom of the C=C bond, as
observed for cis-aconitic acid. 
C 2014 Wiley Periodicals, Inc. Int J Chem Kinet 46: 206215, 2014

INTRODUCTION lent bleaching agents for pulps, and an interaction

In recent years, reactions of tertiary phosphines with
,-unsaturated electrophilic substrates have received
considerable attention in organic chemistry. Stable
products of these transformations, quaternary phos-
phonium salts, attract interest as potential Lewis acidic
catalysts and phase-transfer catalysts [1]. Hydrophilic
hydroxyalkyl phosphines were found to be excel-
Correspondence to: Alexey V. Salin; e-mail: salin555@mail.ru.
Contract grant sponsor: Grants of the President of Russia for
Young Scientists.
Contract grant number: 1316.2012.3.
Supporting Information is available in the online issue at
www.wileyonlinelibrary.com.

C 2014 Wiley Periodicals, Inc.
of such phosphines with conjugated carbonyl com-
ponents of lignin is involved in this process [25].
The Michael-type addition of tertiary phosphines to
activated alkenes, alkynes, and allenes is also a con-
venient way to generate reactive phosphonium zwit-
terionic intermediates, which participate in various
synthetically useful transformations, such as Morita
BaylisHillman and RauhutCurrier reactions, as well
as allenoateacrylate cycloadditions [68]. Although
the spectrum of unsaturated electrophiles that can be in-
volved in such reactions is rather wide, the best results
are generally achieved using unsubstituted substrates
acrylic esters, acrylonitrile, vinyl ketones, etc. Sub-
strates having - and, especially, -substituents re-
quire more forcing reaction conditions, and attempts to
 REACTION OF TRIPHENYLPHOSPHINE WITH ,-UNSATURATED CARBOXYLIC ACIDS
involve them in phosphine-catalyzed transformations
under normal temperature or pressure are usually un-
successful [911]. A number of methods have also been
developed to improve the rate of the MoritaBaylis
Hillman reaction using microwave [12] and ultra-
sound [13] irradiation, Lewis acids [14,15], protic addi-
tives [16,17], ionic liquids [18], etc. Another promising
strategy is based on the concept of hydrogen bonding,
when substrates or catalysts are functionalized in a spe-
cific manner by proton-donor groups [1922]. These
groups are considered to stabilize the resulting zwit-
terion via intramolecular hydrogen bonding with the
carbonyl oxygen of the electron-withdrawing group of
the activated alkene and thus promote the reaction. To
better understand the impact of such an interaction on
the reaction pathway, information about kinetic param-
eters is very valuable.
The current work describes the effect of rate ac-
celeration by neighboring group participation in the
case of the reaction between triphenylphosphine and
unsaturated di- and tricarboxylic acidsmaleic and
cis-aconitic acids; the influence of initial geometry of
the acid on the reaction rate is also discussed. A pre-
requisite for this study was our earlier observation that
maleic acid shows unexpectedly high reactivity in a
reaction with tertiary phosphines, being much more
reactive than its trans-isomer, fumaric acid, and also
the sterically unhindered acrylic acid [23]. Synthetic
aspects of these reactions have been studied in detail
previously [24]. To rationalize the unusual behavior
of maleic acid, using spectrophotometry, we studied
the kinetics of the triphenylphosphine reaction with
dimethyl maleate and dimethyl fumarate, as well as
with cis/trans-aconitic acids in acetic acid media, un-
der the pseudofirst-order condition with respect to
the phosphine. This investigation provides interesting
stereochemical information about the phosphonium
zwitterionic intermediates involved, as well as giving
an example of the effect of anchimeric assistance in
nucleophilic addition reactions.
EXPERIMENTAL
Materials
cis/trans-Aconitic acids were obtained from Sigma
Aldrich (Buchs, Switzerland), whereas all other chem-
icals were from Acros Organics (Geel, Belgium).
Both of the aconitic acids were purified by recrys-
tallization from acetonitrile. In the case of cis-aconitic
acid, heating was avoided to prevent thermal isomer-
ization into trans-aconitic acid. Maleic and fumaric
acids were purified by recrystallization from absolute
International Journal of Chemical Kinetics DOI 10.1002/kin.20842
207
ethanol and water, respectively. Dimethyl maleate was
redistilled under reduced pressure immediately before
use; dimethyl fumarate was purified by recrystalliza-
tion from methanol. Acetic acid (ACS reagent) and
PPh3 were used as received from Acros Organics.
Kinetic Studies
Kinetics were carried out by a spectrophotometric
method under the pseudofirst-order condition with
respect to triphenylphosphine. The general method of
studying the reaction kinetics has been described in
detail previously [25]. Reactions were monitored as a
function of time at 310 nm (for dimethyl fumarate and
trans-aconitic acid), at 300 nm (for dimethyl maleate
and cis-aconitic acid), and at 290 nm for all other
cases up to 80% conversion of PPh3 . Representative
examples of the kinetic methodology are given in the
Supporting Information.
RESULTS AND DISCUSSION
On the basis of kinetic and theoretical studies, we previ-
ously proposed a mechanism for a reaction of tertiary
phosphines with unsaturated carboxylic acids in the
medium of aprotic and protic solvents [2628] similar
to that in Scheme 1.
It involves the initial reversible addition of nucle-
ophilic tertiary phosphine to an activated = bond
of the acid, to form a zwitterionic intermediate with
an equilibrium constant K = k1 /k1 (k1  k1 ). The
next rate-determining step is concerted intermolecu-
lar proton transfer from the protic solvent or second
molecule of unsaturated acid to the generated carban-
ion center with a rate constant k2 . When acetic acid is
used as a solvent, the reaction is first order in phos-
phine, unsaturated acid and acetic acid, third order
overall; thus, the rate is expressed by Eq. (1):
Rate = Kk2 [PR3 ][unsaturated acid][AcOH]
= kIII [PR3 ][unsaturated acid][AcOH] (1)
where kIII is the measured third-order rate constant.
We have also shown that this mechanism is gen-
eralizable to functional derivatives of unsaturated car-
boxylic acids (esters, amides, nitriles), when reactions
are carried out in the presence of a proton-donor source,
for example, in the medium of acetic acid [25]. The
proposed mechanism explains well the observed high
reaction sensitivity to substituent effects (see Table I).
For example, alkyl groups in the -position, as in
the case of methacrylic and itaconic acids, destabilize
208 SALIN ET AL.

Scheme 1 Proposed mechanism for a reaction of tertiary phosphines with unsaturated carboxylic acids in aprotic and protic
solvents.

Table I Third-Order Rate Constants and Activation Parameters for the PPh3 Reaction with Unsaturated Carboxylic
Acids and Related Methyl Esters (30 C)

103 kIII H= S=

Entry Acid (M2 s1 ) (kJ mol1 ) (J mol1 K1 )
1 Acrylic R1 =R2 =R3 =H 8.17 0.16 35 168
2 Methacrylic R1 =R2 =H; R3 =Me 0.163 0.003 45 168
3 Itaconic R =R =H; R =CH2 CO2 H
1 2 3 2.87 0.03 41 157
4 Maleic R1 =R3 =H; R2 =CO2 H 99.5 0.8 31 163
5 Fumaric R1 =CO2 H; R2 =R3 =H 3.12 0.04 34 180
6 cis-Aconitic R =H; R2 =CO2 H; R3 =CH2 CO2 H
1 3.32 0.06 39 164
7 trans-Aconitic R1 =CO2 H; R2 =H; R3 =CH2 CO2 H 0.134 0.006 35 207
8 Crotonic R1 =Me; R2 =R3 =H 0.038 0.001 45 180
9 Tiglic R1 =R3 =Me; R2 =H (0)a

Ester

10 Methyl acrylate R1 =R2 =R3 =H 0.884 0.010 41 169

11 Methyl methacrylate R1 =R2 =H; R3 =Me 0.028 0.001 44 187
12 Dimethyl itaconate R1 =R2 =H; R3 =CH2 CO2 Me 0.268 0.005 44 167
13 Dimethyl maleate R1 =R3 =H; R2 =CO2 Me 0.123 0.003 39 190
14 Dimethyl fumarate R1 =CO2 Me; R2 =R3 =H 0.189 0.006 39 188
a
kIII 106 M2 s1 .

generated carbanion charge and reduce reaction rates
by about 50 and 3 times, respectively, as compared
with acrylic acid (see Table I). -Substituents, both
electron donor and acceptor, as in the case of cro-
tonic and fumaric acids, decrease the reaction rate (by
about 215 and 3 times, respectively) due to screening of
the reaction center, which retards nucleophilic attack
by the phosphine. Tiglic acid, which has the methyl
group at both the - and -positions, exhibits very low
reactivity, which makes precise determination of the
rate constant for this acid complicated. However, the
high reactivity of maleic acid cannot be understood by

International Journal of Chemical Kinetics DOI 10.1002/kin.20842

 REACTION OF TRIPHENYLPHOSPHINE WITH ,-UNSATURATED CARBOXYLIC ACIDS 209

Figure 1 Hypothetic energy profile for the PPh3 reaction

with maleic and fumaric acids involving identical intermedi- Scheme 2 A variant of conformationally isomeric zwitte-
ates on the pathway. rions generated from maleic and fumaric acids.

taking into account only the electronic and steric ef-
fects of its -carboxyl group. This indicates that an-
other substituent effect drives the reaction and reduces
its energy barrier.
One can attribute the difference in reactivities of fu-
maric and maleic acids to destabilization of the initial
state of the latter acid, caused by the thermodynami-
cally less favorable cis-orientation of carboxyl groups
around the C=C bond. If both acids afforded the same
zwitterionic intermediate A in different conformations,
which enables free rotation around the C C single
bond (Scheme 2), the higher starting energy level of
maleic acid would facilitate its interaction with the
= =
phosphine (G2 > G1 ; see Fig. 1).
However, this hypothesis still does not answer the
question: Why is maleic acid even more reactive than
unsubstituted acrylic acid? Moreover, comparison of
relative reactivities of maleic and fumaric esters, as will
be discussed below, argues against the assumption that
the difference in reaction rates of cis/trans-isomers is
determined exclusively by inequality in starting energy
levels of unsaturated substrates.
Most likely, the unusual reactivity of maleic acid
comes from additional stabilization of the result-
ing zwitterions, by an intramolecular hydrogen bond
within a seven-membered ring, in which carbonyl oxy-
gen of the -carboxyl group attached to carbanion cen-
ter acts as a proton acceptor and the -carboxyl group
acts as a proton donor (Fig. 2, I).
Previous kinetic studies showed that intermolecu-
lar hydrogen bonding can greatly increase the reaction
rate, when anionic charge is involved in delocalization
within an eight-membered ring with a solventacetic
acid (Fig. 2, II) [25]. For this reason, carboxylic acids
are about 10 times more reactive than, for example,
related methyl esters, for which the possibility to form
cyclic associates with acetic acid is lost (Fig. 2, III).
Evidently, a similar effect of rate acceleration can be
achieved by means of intramolecular H bonding, as
observed for maleic acid. However, no installation of
a second carboxyl group to the molecule of unsatu-
rated acid results in a rate increase, as exemplified
by relatively low reactivity of fumaric acid. This im-
plies that rotation around the single C C bond in
generated zwitterions is not free, and the difference
between the two intermediates is not conformational.
Restricted rotation around this bond can be attributed
to an intramolecular electrostatic interaction between
the phosphonium center and the carbonyl oxygen of
the carboxyl group participating in delocalization of

Figure 2 Stabilization of phosphonium zwitterions by I: intramolecular H bonding, II: intermolecular H bonding with acetic
acid within a cyclic complex, and III: intermolecular H bonding with acetic acid within an acyclic complex.

International Journal of Chemical Kinetics DOI 10.1002/kin.20842

210 SALIN ET AL.
Scheme 3 Phosphonium zwitterions derived from carbonyl-containing alkenes and acrylonitrile.
Figure 3 Theoretically possible isomeric structures of
zwitterion generated from tertiary phosphine and acrylic
acid.
carbanion charge. The presence of such a P+ O in-
teraction follows from previous experimental and the-
oretical observations:
i) The rate of quaternization of triphenylphos-
phine with acrylonitrile in the medium of
acetic acid is lower than with less electrophilic
substrates activated by carbonyl-containing
electron-withdrawing groups (CO2 H, CO2 Me,
CO2 NH2 ) [25]. According to the rate law equa-
tion (1), the impossibility of PN interaction via
a nitrile group (Scheme 3) increases the decom-
position constant k1 , which reduces the overall
rate constant kIII .
ii) Quantum chemical calculations showed a great
energetic preference in formation of isomeric
zwitterion B, which allows realization of the in-
tramolecular PO interaction (Fig. 3) [28].
The initial geometry of maleic acid favors stabi-
lization of enantiomeric zwitterions formed via nucle-
ophilic attack of phosphine on a stereogenic -carbon
atom, both by an electrostatic PO interaction and in-
tramolecular hydrogen bonding (Scheme 4, structures
C and C ). At the same time, the PO interaction in
zwitterions derived from fumaric acid hinders free ro-
tation around the C C bond, making stabilization by
intramolecular hydrogen bonding impossible for both
enantiomers (Scheme 4, structures D and D ). As a re-
sult, fumaric acid is 32 times less reactive than maleic
acid, and its rate constant is predictable from electronic
and steric substituent effects.
To assess the presented hypothesis, we studied the
kinetics of the reaction of PPh3 with dimethyl maleate
and dimethyl fumarate (Scheme 5), using acetic acid
as a solvent, since intramolecular hydrogen bonding in
esters a priori is impossible.
Interestingly, the study revealed that maleic ester
is about 1.5 times less reactive than fumaric ester
in this reaction. A comparison of rate constants for
several unsaturated acids and their related esters (i.e.,
kIII (1)/kIII (10), kIII (2)/kIII (11), etc.; see Table I), shows
that the ratio is within a range of about 616 units,
whereas the reaction rate for dimethyl maleate is 809
times lower than that for maleic acid. Replacement of
an ester group by a carboxyl group in fact enables a role
of internal reaction catalysis, when the rate is only im-
proved by structural features of the substrate, without
adding any foreign substances.
A rate increase due to neighboring group partici-
pation is known as anchimeric assistance or synartetic
acceleration. This is a general chemical phenomenon
covering reactions of various mechanisms [2931] and
is also typical for enzymatic reactions, effecting a com-
plementary reduction of their energy barriers [32,33].
A well-known example of anchimeric assistance in nu-
cleophilic substitution reactions is the hydrolysis of
yperite (also known as mustard gas), in which a lone
electron pair of the heteroatom in the -position rel-
ative to the leaving group attached to the -carbon
atom generates a three-membered ring that extremely
facilitates the reaction (Scheme 6).
Anchimeric assistance plays a very important role
in deciphering reaction mechanisms, since it pro-
vides unique stereochemical information about the
intermediates involved, which is usually unavailable
from other kinetic data. The finding of anchimeric
assistance for maleic acid strongly suggests that
an intramolecular PO interaction has a significant
impact on the energy profile taking part in stabi-
lization of phosphonium zwitterions when they ap-
pear in a reaction pathway. Precisely, this interac-
tion forms a pseudofive-membered ring containing
a pentacoordinated phosphorus atom, and within the
International Journal of Chemical Kinetics DOI 10.1002/kin.20842
 REACTION OF TRIPHENYLPHOSPHINE WITH ,-UNSATURATED CARBOXYLIC ACIDS 211

Scheme 4 Proposed difference between zwitterions generated from PPh3 and maleic/fumaric acids. (Both enantiomers for
each acid are shown.)

fumaric ester. According to Bents rule of apicophilic-

Scheme 5 Quaternization of PPh3 with dimethyl maleate
and dimethyl fumarate in acetic acid.
cycle rotation around single C C bond becomes
hindered.
To date, there are antagonistic viewpoints expressed
in the literature on the problem of the PO interaction
in phosphonium zwitterions: some authors believe that
it is a key component to stabilize intermediates [34],
whereas others hold the opposite view [35]. All our
previous results and the data presented here are consis-
tent with the first concept, which is also able to explain
lower reactivity of maleic ester in comparison with
ity, a more electronegative carbonyl oxygen atom occu-
pies an apical position in the trigonal bipyramidal envi-
ronment of a pentacoordinated phosphorus atom [36].
Consequently, a new PC bond formed via attack of
phosphine must take an equatorial position. The differ-
ence between two zwitterions generated from dimethyl
maleate (E) and dimethyl fumarate (F) is shown in
Fig. 4.
Forced synperiplanar orientation of the equatorial
phenyl substituent and the carbomethoxy group in
structure E is energetically less favorable than their
anticlinal orientation in structure F. Higher torsional
strain in the first structure increases the decomposi-
tion rate k1 , making the overall constant kIII smaller,
despite the fact that the CO2 Me groups on the same
side of the double carboncarbon bond make dimethyl
maleate more polar than dimethyl fumarate, which

Scheme 6 Anchimeric assistance in hydrolysis of yperite.

International Journal of Chemical Kinetics DOI 10.1002/kin.20842

212 SALIN ET AL.
Figure 4 Spatial structures of phosphonium zwitterions generated from dimethyl maleate (E) and dimethyl fumarate (F).
must promote nucleophilic attack of the phosphine
(i.e., increase the rate constant k1 ). This conclusion
correlates with previous results [25] showing that elec-
trophilicity of the substrate is not the main factor gov-
erning the rate of quaternization. Such a situation be-
comes possible when the rate-determining step is pro-
ton transfer, since if nucleophilic attack was the rate-
determining step, the experimental rate constant would
depend only on the microscopic constant k1 . More
rapid quaternization of PPh3 with dimethyl fumarate
conflicts with the hypothesis that increased reactivity
of maleic acid arises from a higher starting energy level
of this acid, as mentioned above.
Notably, itaconic acid is one more substrate in which
a second carboxyl group, similarly to fumaric acid,
does not lead to a rate increase. This follows from
the ratio kIII (3)/kIII (12) = 11, close enough to that for
acrylic and methacrylic acids (see Table I). Explanation
for this fact can again be found from consideration of
spatial structure of the generated zwitterion implying
the presence of a PO interaction.
The only possible intramolecular hydrogen bond
here does not involve into an interaction as a proton
acceptor the carbonyl oxygen of the carboxyl group
attached to the carbanion center, and therefore does
not have an effect on the additional delocalization of
anionic charge (Fig. 5, I). In this case, stabilization of
the zwitterion by intermolecular hydrogen with acetic
acid seems to be more preferable (Fig. 5, II).
The unusual reactivity of maleic acid encouraged
us to examine, whether the effect of anchimeric as-
sistance can be found in other substrates. With this
aim, we studied kinetics of PPh3 with tricarboxylic
cis/trans-isomeric aconitic acids in the medium of
acetic acid. Again, cis-isomeric acid exhibited sig-
nificantly higher reactivity than trans-isomeric acid,
International Journal of Chemical Kinetics
the ratio kIII (6)/kIII (7) = 25, rather similar to maleic
acid: kIII (4)/kIII (5) = 32 (see Table I). Taking itaconic
acid as a reference, inclusion of a cis-carboxyl group
slightly improves the reaction rate (kIII (6)/kIII (3) =
1.2), although the steric effect of a -substituent must
inhibit addition of phosphine, as observed for trans-
aconitic and fumaric acids. Therefore, the effect of
anchimeric assistance also takes place in cis-aconitic
acid; however, it is much weaker than for maleic acid,
since kIII (4)/kIII (1) = 12. Most probably, the reason for
this should be sought from how intramolecular hydro-
gen bonding within the initial structure of the cis-acid
favors or disfavors anchimeric assistance when phos-
phine attacks one of the carbon atoms of the C=C bond.
It is expected that a combination of two interrelated
structural factors maximize the effect of acceleration:
i) an s-cis-conformation of the C=C bond and the
C=O group participating in delocalization of
carbanion charge, which makes possible an in-
tramolecular PO interaction;
ii) the -carboxyl group acts as a proton acceptor,
whereas the -carboxyl group acts as a proton
donor, leading to additional delocalization of an-
ionic charge by means of hydrogen bonding.
With consideration of these factors, attack of phos-
phine on the -carbon atom of maleic acid (path b)
is more preferable than -attack (path a), taking into
account equal steric hindrance of the - and -centers
(Scheme 7). According to X-ray data, cis-aconitic acid,
as well as maleic acid, is prone to form an intramolec-
ular hydrogen bond between the two carboxyl groups
attached to the C=C bond, as shown in Scheme 7,
structure G [37].
DOI 10.1002/kin.20842
 REACTION OF TRIPHENYLPHOSPHINE WITH ,-UNSATURATED CARBOXYLIC ACIDS 213

Figure 5 Structures of the zwitterion derived from PPh3 and itaconic acid involving intramolecular (I) and intermolecular
(II) H-bonding.

Scheme 7 Influence of intramolecular hydrogen bonding in maleic and cis-aconitic acids on the readiness of PPh3 addition.

However, owing to the steric effect of the CH2 CO2 H
group, attack toward the -carbon atom is strongly
retarded (high reaction sensitivity to substituent ef-
fects was discussed earlier), but attack on the -carbon
atom violates both factors that can contribute to effi-
cient stabilization of the generated zwitterion. To over-
come such unfavorable situation, reorganization of the
intramolecular hydrogen bond is necessary to make
the -carboxyl group a proton acceptor, and the -
carboxyl group a proton donor (structure H, Scheme 7).
Evidently, the need of such isomerization within cis-
aconitic acid (or the intermediate formed) decreases
the reaction rate and the effect of anchimeric assis-
tance in comparison with maleic acid, in which an
intramolecular bond initially assists interaction with
tertiary phosphine.

International Journal of Chemical Kinetics DOI 10.1002/kin.20842

214 SALIN ET AL.
Notably, enthalpies of activation for reactions of
fumaric and trans-aconitic acids are not high (com-
pare 5 with 1; 7 with 3 and 6 in the table), and
small rate constants are compensated by more nega-
tive values of entropy of activation. Apparently, this
is due to transformation of the initially formed less
stable zwitterion to the corresponding isomer aris-
ing from maleic or cis-aconitic acids having more
favorable arrangement of substituents. The exother-
mic effect of such isomerization partially compensates
for the enthalpy barrier of the reaction, but this ad-
ditional step requiring an intermediate with a more
ordered structure results in an increased entropy of
activation.
CONCLUSIONS
The effect of anchimeric assistance was revealed for
maleic and cis-aconitic acids in the course of kinetic
studies of the quaternization of triphenylphosphine
with ,-unsaturated carboxylic acids in the medium
of acetic acid. Using esters of maleic and fumaric acids,
we have shown that this effect arises from additional
stabilization of reaction intermediates by intramolec-
ular hydrogen bonding, which involves an interaction
of the cis-carboxyl group of the acid. The difference
in reactivities of cis/trans-isomeric substrates provides
evidence of a crucial role of the intramolecular PO in-
teraction in stabilizing phosphonium zwitterions. The
kinetic data obtained provide additional evidence to
support the proposed mechanism for this reaction that
involves initial formation of a zwitterionic intermedi-
ate, followed by rate-determining proton transfer to
the generated carbanion center. This study sheds light
on important structural features of key intermediates
of phosphine-catalyzed reactions of unsaturated elec-
trophilic reagents, the direct isolation and characteri-
zation of which still remain an elusive goal. The in-
formation obtained can be used in the further devel-
opment of methodologies for improving phosphine-
catalyzed reaction rates by neighboring group
participation.
The effect of anchimeric assistance in maleic acid
is much stronger than in cis-aconitic acids, since re-
organization of intramolecular hydrogen bonding in
the latter acid in necessary to achieve efficient sta-
bilization of the intermediate. Interestingly, the fact
that maleic acid, in contrast to fumaric acid, cannot
be found in natural materials [38], may be explained
in terms of pronounced anchimeric assistance to its
rapid participation in nucleophilic addition reactions
in vivo.
International Journal of Chemical Kinetics
SUPPORTING INFORMATION
A representative procedure for the determination of
kinetic and activation parameters on the example of
the Ph3 P reaction with dimethyl maleate, including ab-
sorbance vs. time data and the corresponding ln plots,
a plot showing kinetic dependences, and an Arrhenius
plot are presented.
Generous financial support from Dr. Alexandr Kuzmin is
greatly acknowledged. We also thank Prof. Ethan Taylor for
helpful discussions.
BIBLIOGRAPHY
1. Werner, T. Adv Synth Catal 2009, 351, 14691481.
2. Moiseev, D. V.; James, B. R.; Hu, T. Q. Inorg Chem
2007, 46, 47044712.
3. Moiseev, D. V.; Patrick, B. O.; James, B. R.; Hu, T. Q.
Inorg Chem 2007, 46, 93899399.
4. Moiseev, D. V.; James, B. R.; Gushchin, A. V. Russ J
Gen Chem 2012, 82, 840847.
5. Moiseev, D. V.; James, B. R.; Gushchin, A. V. Phospho-
rus Sulfur Silicon 2013, 188, 678690.
6. Basavaiah, D.; Reddy, B. S.; Badsara, S. S. Chem Rev
2010, 110, 54475674.
7. Aroyan, C. E.; Dermenci, A.; Miller, S. J. Tetrahedron
2009, 65, 40694084.
8. Ye, L.-W.; Zhou, J.; Tang Y. Chem Soc Rev 2008, 37,
11401152.
9. Jenner, G. Tetrahedron Lett 2000, 41, 30913094.
10. Shi, Y.-L.; Xu, Y.-M.; Shi, M. Adv Synth Catal 2004,
346, 12201230.
11. Shi, Y.-L.; Shi, M. Tetrahedron 2006, 62, 461475.
12. de Souza, R. O. M. A.; Miranda, L. S. M. Mini-Rev Org
Chem 2010, 7, 212220.
13. Coelho, F.; Almeida, W. P.; Veronese, D.; Mateus, C. R.;
Lopes, E. C. S.; Rossi, R. C.; Silveira, G. P. C.; Pavam
C. H. Tetrahedron 2002, 58, 74377447.
14. Tang, H.; Cheng, X.; Zhang, Z. Phosphorus Sulfur Sili-
con 2012, 187, 815.
15. Johnson, C. L.; Donkor, R. E.; Nawaz, W.; Karodia N.
Tetrahedron Lett 2004, 45, 73597361.
16. Luo, S.; Zhang, B.; He, J.; Janczuk, A.; Wang, P. G.;
Cheng, J.-P. Tetrahedron Lett 2002, 43, 73697371.
17. Aggarwal, V. K.; Fean, D. K.; Mereu, A.; Williams, R.
J Org Chem 2002, 67, 510514.
18. Portoa, R. S.; Amarantea, G. W.; Cavallaroa, M.; Poppib,
R. J.; Coelho, F. Tetrahedron Lett 2009, 50, 11841187.
19. Ameer, F.; Drewes, S. E.; Freese, S.; Kaye, P. T. Synth
Commun 1988, 18, 495500.
20. Drewes, S. E.; Freese, S.; Emslie, N. D.; Roos, G. H. P.
Synth Commun 1988, 18, 15651572.
21. Basavaiah, D.; Sarma, P. K. S. Synth Commun 1990, 20,
16111615.
DOI 10.1002/kin.20842
 REACTION OF TRIPHENYLPHOSPHINE WITH ,-UNSATURATED CARBOXYLIC ACIDS
22. Marinetti, A.; Voituriez, A. Synlett 2010, 174
194.
23. Galkin, V. I.; Salin, A. V.; Bakhtiyarova, Y. V.; Sobanov,
A. A. Russ J Gen Chem 2009, 79, 919924.
24. Galkin, V. I.; Bakhtiyarova, Y. V.; Sagdieva, R. I.; Galk-
ina, I. V.; Cherkasov, R. A. Heteroatom Chem 2006, 17,
557566, and references therein.
25. Salin, A. V.; Fatkhutdinov, A. R.; Ilin, A. V.; Sotov,
E. I.; Sobanov, A. A.; Galkin, V. I.; James, B. R. J Phys
Org Chem 2013, 26, 675678.
26. Salin, A. V.; Sobanov, A. A.; Bakhtiyarova, Y. V.;
Khabibullin, A. A.; Galkin, V. I. Russ J Gen Chem 2010,
80, 17381742.
27. Salin, A. V.; Sobanov, A. A.; Bakhtiyarova, Y. V.;
Khabibullin, A. A.; Galkin, V. I. Russ J Gen Chem 2011,
81, 824830.
28. Salin, A. V.; Aminova, R. M.; Galkin, V. I. Int J Quantum
Chem 2013, 113, 10861094.
29. Mora, J. R.; Lezama, J.; Berroteran, N.; Cordova, T.;
Chuchani, G. Int J Quantum Chem 2012, 112, 3729
3738.
International Journal of Chemical Kinetics DOI 10.1002/kin.20842
215
30. Ohwada, T.; Tani, N. Sakamaki, Y.; Kabasawa, Y.; Otani,
Y.; Kawahata, M.; Yamaguchi, K. Proc Natl Acad Sci
2013, 110, 42064211.
31. Khong, S.N.; Kwon, O. Molecules 2012, 17, 5626
5650.
32. Maiti, M.; Michielssens, S.; Dyubankova, N.; Maiti, M.;
Lescrinier, E.; Ceulemans, A.; Herdewijn, P. Chem Eur
J 2012, 18, 857868.
33. Fibriansah, G.; Gliubich, F. I.; Thunnissen, A.-M. W. H.
Biochemistry 2012, 51, 91649177.
34. Liang, Y.; Liu, S.; Xia, Y.; Li, Y.; Yu, Z.-X. Chem Eur J
2008, 14, 43614373.
35. Krafft, M. E.; Haxell, T. F. N.; Seibert, K. A.; Abboud,
K. A. J Am Chem Soc 2006, 128, 41744175.
36. Kumara Swamy, K. C.; Satish Kumar, N. Acc Chem
Res 2006, 39, 324333, and references therein.
37. Nagel, N.; Endruschat, U.; Bock, H. Acta Crystallogr,
Sect C: Cryst Struct Commun 1996, 52, 29122915.
38. Lohbeck, K.; Haferkorn, H.; Fuhrmann, W.; Fedtke,
N. Ullmanns Encyclopedia of Industrial Chemistry;
Wiley-VCH: Weinheim, Germany, 2000; pp 145155.