Functionalized mercaptoacetic and propionic acid amides: synthesis, cyclopalladation features, and catalytic activity of metal complexes

Article abstract of DOI:10.1007/s11172-015-1207-9

Upon treatment with thiophenol or neomenthyl mercaptane, chloroacetand propionamides with an additional Nor S-donor substituent in the amine part gave new multidentate ligands readily undergoing direct cyclopalladation in the reaction with PdCl₂

Full text of DOI:10.1007/s11172-015-1207-9

Russian Chemical Bulletin, International Edition, Vol. 64, No. 11, pp. 2678—2689, November, 2015
2678
Functionalized mercaptoacetic and propionic acid amides:
synthesis, cyclopalladation features, and catalytic activity of metal complexes*
S. G. Churusova,a D. V. Aleksanyan,a Z. S. Klemenkova,a Yu. V. Nelyubina,a
O. I. Artyushin,a A. A. Vasil´ev,b V. A. Kozlov,a D. V. Sudarikov,c and S. A. Rubtsovac
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: fos@ineos.ac.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328
cInstitute of Chemistry, Komi Scientific Center of the Ural Branch of the Russian Academy of Sciences,
48 ul. Pervomaiskaya, 167982 Syktyvkar, Russian Federation.
Fax: +7 (821 2) 21 8477
Upon treatment with thiophenol or neomenthyl mercaptane, chloroacetꢀ and propionꢀ
amides with an additional Nꢀ or Sꢀdonor substituent in the amine part gave new multidentate
ligands readily undergoing direct cyclopalladation in the reaction with PdCl2(NCPh)2. The
3
realization of κ ꢀX,N,Sꢀcoordination (X = N, S) in the complexes obtained was confirmed by
IR and NMR spectroscopy and, in some cases, by singleꢀcrystal Xꢀray crystallography. The
evaluation of catalytic activity of the palladocycles in the Suzuki crossꢀcoupling of aryl bromides
with PhB(OH)2 allowed us to establish the principal structure—activity correlations.
Key words: palladium(II) complexes, carboxamides, sulfides, sulfoxides, cyclopalladation,
catalytic activity, Suzuki crossꢀcoupling.
Progress in coordination chemistry is mainly deterꢀ
mined by the development of new types of ligand systems,
where directed synthesis of structures with certain geoꢀ
metric and electronic properties remains a key issue. In
this respect, multidentate ligands with readily tunable
structures are of special interest. Such systems inꢀ
clude functionally substituted carboxamides with additional
Nꢀ, Pꢀ, and Sꢀdonor centers in both the acid and amine
moieties. Among ligands with nitrogenꢀcontaining auxilꢀ
iary donor center pyridineꢀ2ꢀcarboxamides (picolinaꢀ
mides) capable of serving as Nꢀmonoanionic or neutral
ligands1 are the most popular ones. The introduction of
substituents with additional coordination active fragment
into the amine part enabled the synthesis of new types of
metal chelates with different geometry around the metal
center and, as a consequence, different physicochemical
properties,2 for example, complexes with high catalytic
activity in different reactions,3 as well as convenient models
for investigation of metal ion binding modes in biochemiꢀ
cal systems.4 Apart from picolinamides, where the nitrogen
atom of the heterocycle plays the role of one of the donor
centers upon complexation with different metals, there
are also described benzoic acid derivatives having ortho
substituents with the phosphorus atom capable of perꢀ
forming this function. The complexes of such ligands are
widely used as catalysts5 and radiopharmaceuticals.6
As to carboxamides with an additional Sꢀdonor center,
there are literature data on the synthesis and coordinating
ability of only mercaptoacetic acid derivatives. These comꢀ
pounds can exhibit monoꢀ7 or bidentate8 coordination
mode without participation of the amide nitrogen atom.
The examples of multidentate analogues of mercaptoacetꢀ
amides are limited to only several compounds with an
additional pyridine fragment.9 At the same time, recently
we have shown that palladium(II) S,N,Oꢀcomplexes based
on (thio)phosphorylacetamides with an additional coorꢀ
dination active P(X) group (X = O, S) feature high cataꢀ
lytic activity in the Suzuki reaction.10
In continuation of our studies on the synthesis of multiꢀ
dentate ligands, in the present work we synthesized new
functionally substituted mercaptoacetic and propionic acid
amides with a flexible aliphatic framework, in which the
sulfur or nitrogen atoms of substituents in the amine comꢀ
ponent serve as the additional coordination sites, as well
as studied peculiarities of their direct cyclopalladation and
catalytic activity of the resulting metal complexes in
the model Suzuki reaction.
* To 90th birthday anniversary of the Corresponding Member of the
Russian Academy of Sciences T. A. Mastryukova (1925—2006).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2678—2689, November, 2015.
1066ꢀ5285/15/6411ꢀ2678 © 2015 Springer Science+Business Media, Inc.

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2679
The target ligands (Scheme 1) were synthesized by the
reaction of chloroacetyl chloride with functionalized
amines, followed by thiophenolysis of the intermediate
chloroacetamides 1a—d under action of in situ generated
PhSK. 2ꢀAminomethylꢀ and 2ꢀaminoethylpyridines,
8ꢀaminoquinoline, and 2ꢀ(diphenylthiophosphoryl)aniline
were chosen as the amine components. This allowed us to
obtain ligands 2a—d differing not only in the nature of
additional coordination sites (the nitrogen atom of the
heterocycles or the sulfur atom of the thiophosphoryl
group), but also in the flexibility of spacers between the
auxiliary donor group and the amide fragment (a flexible
aliphatic spacer in compounds 2a,b or a rigid aromatic
spacer in 2c,d).
unit between the thioether group and the amide fragment
(see Scheme 2). The reaction of 3ꢀchloropropionyl chloꢀ
ride with oꢀ(diphenylthiophosphoryl)aniline gave, together
with the target chloroꢀsubstituted amide 5, also the correꢀ
sponding acrylanilide. Note that the use of chiral neoꢀ
menthylmercaptane allowed us to obtain target ligands 3
and 4 in the enantiomerically pure form.
The IR spectra of the crystalline samples of amides
2a—d, 3, and 4 exhibit, together with the stretching vibraꢀ
tions of the carbonyl group (ν = 1643—1702 cm–1) and
the N—H bond (ν = 3201—3330 cm–1), also the absorpꢀ
tion bands characteristic for the secondary amide group,
which are mainly attributed to the bending vibrations of
the NH fragment (ν = 1503—1546 cm–1). The characterꢀ
istic absorption bands of the thiophosphoryl functional
group in compounds 2d, 3, and 4 were found in the region
Scheme 1
1
of ~635 cm–1. The H NMR spectra of all the amides
obtained, apart from the signals of the aliphatic and aroꢀ
matic protons, also contain the downfeild signals characꢀ
teristic for the NH protons (δH = 7.65—11.12). The
13C NMR spectra can be easily interpreted and also conꢀ
firm the structure of the compounds obtained. For thioꢀ
phosphorylꢀsubstituted amides 2d, 3, and 4, the singlets of
the phosphorus atoms in the 31P NMR spectra were
found in the region characteristic for phosphine sulfides
(δP = 39.59—40.17).
The reaction of ligands 2a—d with PdCl2(NCPh)2 in
dichloromethane at ~20 °C readily proceeded as the metꢀ
allation of the amide group with concomitant coordinaꢀ
tion by the metal atom of the auxiliary Nꢀ and Sꢀdonor
groups, leading to κ3ꢀN,N,Sꢀ and κ3ꢀS,N,Sꢀpalladocycles
6a—d in high yields (Scheme 3). Complexes 7 and 8 with
the neomenthyl substituent at the sulfur atom of the thioꢀ
ether group were obtained under similar conditions. The
products were obtained in high yields independent from
the size of the formed fused metallocycles (from 5,5ꢀ to
6,6ꢀmembered complexes). Note that in the case of phosꢀ
phorusꢀsubstituted ligands 2d, 3, and 4, the cyclopalladaꢀ
tion smoothly proceeded in the absence of a base, whereas
for the heterocyclic derivatives 2a—c it was necessary to
add Et3N in order to accelerate the complexation and
increase the yields of the target metal complexes.
Treatment of chloroacetamide 1d with potassium deꢀ
rivatives of neomenthylmercaptane led to the formation of
functionalized amide 3 with an alicyclic substituent at the
sulfur atom of the thioether group (Scheme 2). To comꢀ
pare the complexation abilities, we also synthesized its
analogue S,N,Sꢀligand 4 with an additional methylene
Scheme 2

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Churusova et al.
Scheme 3
Complexes 6a—d, 7 and 8 are brightly colored, moisꢀ
ture stable compounds with high decomposition points.
Their structures and compositions were unambiguously
confirmed by elemental analysis, IR and NMR spectroscopy,
and, in some cases, by singleꢀcrystal Xꢀray crystallograꢀ
phy. The absence of the downfield signals of the hydrogen
complexes 6a—d in CDCl3 at ~20 °C as a mixture of stable
atropoisomers. The 13C NMR spectrum of complex 6d
based on the thiophosphorylꢀsubstituted ligand also has
a double set of signals for the carbon atoms of the phenyl
rings in the Ph2P(S) group. The introduction of a chiral
neomenthyl substituent allowed us to obtain κ3ꢀS,N,Sꢀ
palladocycles as a mixture of diastereomers, which have
different signals for the phosphorus and carbon atoms in
the 31P and 13C NMR spectra, respectively, like in the
case of 3ꢀmercaptopropionic acid derivative 8, or differing
in the signals for the carbon atoms only in the acid comꢀ
ponent, like in the case of compound 7 with a shortened
aliphatic spacer between the thioether group and the amide
fragment. The differences in the ratio of isomers (1 : 2 (7),
1 : 3 (8)), apparently, is due to the preferable formation
of different forms, which requires further detailed invesꢀ
tigation.
1
atom of the amide group in the H NMR spectra of all
the complexes obtained indicates the occurrence of metꢀ
allation. The IR spectra of the complexes do not have
absorption bands corresponding to the stretching or bendꢀ
ing vibrations of the NH fragment, whereas the absorption
band of the carbonyl group is considerably shifted to the
lowꢀfrequency region relative to the IR spectra of the
free ligands (Δν = 29—96 cm–1). The downfield shift of
the signals of the protons at the tertiary carbon atoms
ortho to the Nꢀdonor atom in the pyridine (ΔδH
=
= 0.36—0.74 ppm) or quinoline ring (ΔδH = 0.13 ppm), in
1
the H NMR spectra of complexes 6a—c relative to the
The structures of complexes 6b—d and 8 were conꢀ
firmed by the data of singleꢀcrystal Xꢀray diffraction studꢀ
ies (Figs 1—4). The main geometric parameters are given
in Table 1. In all the complexes, the Pd—Cl bond distance
is virtually the same (2.3127(9)—2.3166(15) Å), whereas
spectra of the corresponding ligands is an indirect eviꢀ
dence of coordination of the palladium atom in these
groups. The upfield shift of the signals of the phosphorus
atom in the 31P NMR spectra of palladocycles 6d, 7, and 8
(ΔδP = 1.6—3.4 ppm), together with the lowꢀfrequency
shift of the absorption band characteristic for the P=S group
in the IR spectra (Δν = 27—36 cm–1), indicates the forꢀ
mation of the P(S)—Pd bond. The coordination of the
sulfur atom in the thioether group is indicated by the shift
of the signals for the carbon atom of the methylene unit in
the 13C NMR spectra, with the value and direction of the
shift being dependent on the nature of substituent in the
RS group (R = Ph or neomenthyl). Note that for phenylꢀ
mercapto derivatives, the complexation is accompanied
by a typical change in the splitting pattern of the signals
for the hydrogen atoms of the methylene unit in the acid
Сl(1)
С(12)
С(5)
С(13)
С(4)
С(11)
S(1)
Pd(1)
С(14)
С(1)
С(6)
С(3)
N(2)
С(10)
С(15)
С(2)
С(9)
N(1)
С(7)
С(8)
O(1)
1
component in the H NMR spectra from one singlet to
two doublets or the ABꢀsystem. The diastereotopic nature
of this fragment is due to the formation of the system of
two fused metallocycles, which results in the existence of
Fig. 1. General view of complex 6b. Hereinafter, the nonhydroꢀ
gen atoms are shown as the displacement ellipsoids at a 50%
probability level.

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2681
the Pd—N and Pd—S bond distances vary depending on
both the nature of the Sꢀ and Nꢀdonor centers and the
sizes of fused metallocycles. In N,N,Sꢀcomplexes 6b
and 6c, the Pd—N bond distances with the amide and
pyridine or quinoline nitrogen atom (see Figs 1 and 2,
С(14)
Сl(1)
Pd(1)
С(13)
С(1)
С(15)
С(2)
С(12)
С(16)
N(2)
Table 1) differ by about 0.07 Å, but synchronously inꢀ
crease on going from 5,5ꢀmembered complex 6c to its
analogue with the metallocycles of different sizes (comꢀ
pound 6b). The N,Nꢀmetallocycle in complex 6b has the
twist conformation (with the deviation of atoms C(6) and
N(2) by 0.79 and 0.44 Å from the plane of the other atoms),
whereas the fiveꢀmembered N,Nꢀpalladocycle in comꢀ
pound 6c is planar. There are no significant variations in
the Pd(1)—S(1) bond distances (2.2674(8) Å in 6b and
2.2662(11) Å in 6c) or the conformation of the sulfurꢀ
containing metallocycle (the envelop conformation with
the deviation of atoms C(9) in 6b or C(11) in 6c by 0.44
and 0.39 Å, respectively). In S,N,Sꢀcomplexes 6d and 8
(see Figs 3 and 4, Table 1), the Pd—N and Pd—S bonds
are slightly elongated. The last mentioned bonds, dependꢀ
ing on the nature of the donor sulfur atom (thiophosphorꢀ
yl or thioether group) differ by ~0.02 Å and elongate by
a similar value on going from 5,6ꢀmembered complex 6d
to 6,6ꢀmembered analogue 8. The conformations of
the sulfurꢀcontaining metallocycles vary from halfꢀchair
(fiveꢀmembered metallocycle in complex 8) to boat (in
the other cases). Note that N,N,Sꢀcomplexes 6b,c have
nearly ideal square planar geometry around the metal
atom, whereas in the case of S,N,Sꢀpalladocycles 6d
and 8, the environment of the palladium atom is noticeꢀ
ably distorted: the S(1)—Pd(1)—S(2) angle varies within
170.66—172.261°, whereas atom S(1) deviates by no more
than 0.34—0.40 Å.
С(8)
S(1)
С(17)
С(3)
С(9)
N(1)
С(7)
С(11)
С(10)
С(4)
С(6)
O(1)
С(5)
Fig. 2. General view of complex 6c.
С(4)
С(25)
С(12)
С(5)
С(6)
С(26)
С(21)
С(24)
С(13)
С(14)
Cl(1)
С(3)
С(2)
С(11)
С(10)
С(1)
С(23)
Pd(1)
P(1)
С(22)
С(9)
S(2)
N(1)
С(15)
С(7)
S(1)
С(16)
O(1)
С(17)
С(8)
С(20)
С(19)
С(18)
Fig. 3. General view of complex 6d.
С(19)
С(30)
С(29)
С(4)
С(5)
С(31)
С(26)
С(18)
С(17)
C(3)
С(2)
С(6)
С(12)
С(11)
С(1)
С(28)
Сl(1)
С(27)
P(1)
С(10)
С(13)
S(2)
Pd(1)
С(7)
N(1)
С(15)
С(14)
S(1)
С(20)
С(21)
С(22)
С(16)
O(1)
С(9)
С(25)
С(24)
С(8)
С(23)
Fig. 4. General view of complex 8. The second component of the disordered neomenthyl fragment and two solvent molecules of
tetrachloromethane are omitted.

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Churusova et al.
Table 1. Principal bond lengths (d) and bond angles (ω) in molecules of compounds 6b—d, 8, and 10
Parameter
Value
Parameter
Value
Compound 6с
Parameter
Value
Compound 6b
Compound 8
Bond length
Pd(1)—Cl(1)
Pd(1)—N(1)
Pd(1)—N(2)
Pd(1)—S(1)
N(1)—C(8)
O(1)—C(8)
S(1)—C(9)
Angle
d/Å
Angle
N(1)—Pd(1)—S(1)
S(1)—Pd(1)—Cl(1) 93.52(5)
N(2)—Pd(1)—S(1) 167.20(13)
Compound 6d
Bond length
Pd(1)—Cl(1)
Pd(1)—N(1)
Pd(1)—S(1)
Pd(1)—S(2)
N(1)—C(7)
O(1)—C(7)
S(1)—C(8)
P(1)—S(2)
Angle
ω/deg
84.13(10)
Bond length
O(1)—C(7)
S(1)—C(9)
P(1)—S(2)
Angle
S(2)—Pd(1)—Cl(1) 84.29(6)
S(2)—Pd(1)—N(1)
N(1)—Pd(1)—S(1)
S(1)—Pd(1)—Cl(1) 89.86(6)
N(1)—Pd(1)—Cl(1) 178.01(16)
S(2)—Pd(1)—S(1) 170.66(6)
Compound 10*
Bond length
Pd(1)—Cl(1)
Pd(1)—N(1)
Pd(1)—N(2)
Pd(1)—S(1)
N(1)—C(7)
O(1)—C(7)
S(1)—C(8)
S(1)—O(2)
Angle
N(1)—Pd(1)—Cl(1) 177.70(5)
N(2)—Pd(1)—Cl(1) 95.87(5)
N(1)—Pd(1)—N(2) 81.97(7)
N(1)—Pd(1)—S(1)
S(1)—Pd(1)—Cl(1) 96.785(19)
N(2)—Pd(1)—S(1) 167.27(5)
d/Å
2.3153(8)
1.992(2)
2.070(3)
2.2674(8)
1.350(4)
1.245(4)
1.819(3)
ω/deg
1.256(8)
1.831(7)
2.010(2)
ω/deg
d/Å
2.3127(9)
2.0472(16)
2.2938(9)
2.3111(9)
1.365(2)
1.233(2)
1.8116(19)
2.0176(9)
ω/deg
95.32(16)
90.76(16)
N(1)—Pd(1)—Cl(1) 174.40(7)
N(2)—Pd(1)—Cl(1) 92.93(8)
N(1)—Pd(1)—N(2) 92.48(10)
N(1)—Pd(1)—S(1)
85.36(7)
d/Å
S(1)—Pd(1)—Cl(1) 89.30(3)
N(2)—Pd(1)—S(1) 176.62(8)
Compound 6c
2.3146(5)
1.9629(17)
2.0435(18)
2.2178(5)
1.330(3)
1.242(3)
1.812(2)
1.4669(16)
ω/deg
S(2)—Pd(1)—Cl(1) 85.963(19)
N(1)—Pd(1)—S(2)
N(1)—Pd(1)—S(1)
Bond length
Pd(1)—Cl(1)
Pd(1)—N(1)
Pd(1)—N(2)
Pd(1)—S(1)
N(1)—C(10)
O(1)—C(10)
S(1)—C(11)
Angle
d/Å
98.81(4)
85.37(4)
2.3162(12)
1.964(3)
2.025(4)
2.2662(11)
1.297(5)
1.243(5)
1.793(4)
ω/deg
S(1)—Pd(1)—Cl(1) 90.485(19)
N(1)—Pd(1)—Cl(1) 173.01(4)
S(2)—Pd(1)—S(1) 172.261(18)
Compound 8
Bond length
Pd(1)—Cl(1)
Pd(1)—N(1)
Pd(1)—S(1)
Pd(1)—S(2)
N(1)—C(7)
d/Å
2.3166(15)
2.032(5)
2.3131(15)
2.3338(15)
1.347(8)
N(1)—Pd(1)—Cl(1) 177.00(10)
N(2)—Pd(1)—Cl(1) 97.72(14)
N(1)—Pd(1)—N(2) 84.42(16)
85.36(5)
* The data for one of two symmetrically independent molecules.
Scheme 4
Taking into account an important role in transition
metal chemistry of such weak donor ligands as sulfoxꢀ
ides11, we have chosen ligand 2a as an example to demonꢀ
strate a possibility of the oxidation of the thioether group
with an excess of hydrogen peroxide in anhydrous tertꢀbutyl
alcohol (Scheme 4). It is important to note that under
these conditions the thioether is oxidized to sulfoxide, and
no product of its further oxidation (sulfone) was formed. The
IR spectrum of compound 9, together with the absorption
bands of the functional amide group (ν/cm–1: 1551
(NHCO), 1669 (C=O), 3278 (NH)), exhibits also a strong
absorption band in the region of 1043 cm–1 characteristic
for the stretching vibrations of the S=O bond. In the
13C NMR spectrum, the signals of the carbon atoms of the
methylene unit and the ipsoꢀcarbon atom in the phenyl
ring directly bonded to the sulfoxide group are downꢀ
field shifted relative to the spectrum of the starting sulꢀ
fide 2a (ΔδC = 22.48 and 7.23 ppm, respectively). In the
1H NMR spectrum, the signals for the hydrogen atoms of
the prochiral methylene group in the S(O)CH2 fragꢀ
ment are found as two doublets because of the introducꢀ
tion of the center of asymmetry (the sulfur atom of the
sulfoxide group).
The reaction of ligand 9 with PdCl2(NCPh)2 in dichloroꢀ
methane at ~20 °C in the presence of Et3N also proceeded
as the metallation of the amide group with concomitant
coordination of the nitrogen atom of the pyridine ring and

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2683
the sulfur atom of the sulfoxide fragment, leading to
κ3ꢀN,N,Sꢀcomplex 10 in high yield (see Scheme 4). An atꢀ
tempt to oxidize the sulfanyl group in palladocycle 6a
under conditions similar to those used in the synthesis of
ligand 9 did not give sulfoxide complex 10: the starting
complex 6a was recovered unchanged from the reaction
mixture even after 7 days of the reaction contact.
N(1)—Pd(1)—Cl(1) line with the N(2)—Pd(1)—S(1) anꢀ
gle of 163.41(5)°.
The catalytic activity of palladocycles obtained was
tested in the model Suzuki reaction, the crossꢀcoupling of
aryl bromides with PhB(OH)2 (Scheme 5). For correct
comparison of the results, all the experiments were carried
out under similar conditions: heating in DMF at 120 °C
for 5 h in the presence of K3PO4 as a base. Almost all the
complexes obtained in this work exhibit a high level of
activity in the crossꢀcoupling of 4ꢀbromoacetophenone
(11a) with PhB(OH)2 at the concentration of 1 mol.%
(Table 2). Palladocycles 7 and 8 with the alkyl (neomenꢀ
thyl) substituent at the sulfur atom of the thioether group
were more active than their phenylmercaptoꢀsubstituted
analogue 6d. It was found that upon a decrease in the
concentration of the palladium complexes to 0.1 mol.%,
S,N,Sꢀcomplexes 6d, 7, and 8 afforded a higher level of
conversion of 4ꢀbromoacetophenone than N,N,Sꢀhemiꢀ
labile palladocycles 6a—c and 10 (see Table 2). Note
that the sulfoxide derivative 10 turned out to be more active
(pre)catalyst than its sulfide prototype 6a. An increase in
the catalytic activity was also observed upon elongation of
the aliphatic spacer between the auxiliary donor group
and the amide fragment. Thus, the yield of biaryl 12a
with a 0.1 mol.% of complex 6b based on the aminoethylꢀ
pyridine ligand was 50% versus 25% in the case of its
aminomethylpyridine analogue 6a. At the same time,
complex 8, which is a 3ꢀmercaptopropionic acid derivative,
exhibited higher catalytic activity than palladocycle 7 based
on mercaptoacetamide. In the case of less active 4ꢀbromoꢀ
anisole (11b), most complexes obtained in this work were
revealed to be inefficient: the conversion of 11b was 4—27%
at 1 mol.% concentration of the (pre)catalyst. However,
S,N,Sꢀpalladocycle 8 exhibited a high enough level of
activity in the crossꢀcoupling of 4ꢀbromoanisole with
PhB(OH)2 not only at the catalyst loading of 1 mol.%, but
also upon a tenꢀfold decrease in the concentration of the
palladium (pre)catalyst (75 and 77%, respectively).
1
In the H NMR spectrum, like in the case of sulfide
analogues, the complexation of sulfoxide 9 was accompaꢀ
nied by a characteristic downfield shift of the signal of the
proton at the tertiary carbon atom ortho to the Nꢀdonor
center of the pyridine ring (ΔδH = 0.4 ppm), as well as of
the signal of the carbon atom in the S(O)CH2 fragment
in the 13C NMR spectrum (ΔδC = 10.38 ppm). The IR
spectrum of complex 10 does not exhibit absorption bands
of the stretching or bending vibrations of the NH fragꢀ
ment, which, together with the disappearance of the downꢀ
1
field signal for the amide protons in the H NMR specꢀ
trum, confirms the occurrence of metallation. Apart from
that, the absorption band of the stretching vibrations
of the S(O) group is strongly shifted toward higher
frequencies relative to the IR spectrum of the free ligand
(ν = 1117 cm–1). Complex 10 crystallizes with two
symmetrically independent molecules in the unit cell
(Fig. 5), which differ in both the Pd(1)—S(1) bond disꢀ
tance (2.2178(5) and 2.2214(6) Å) (see Table 1) and the
conformations of the fused metallocycles. Thus, the N,Sꢀ
metallocycle is a flattened envelop with the deviation of
Pd(1) atom by 0.20 Å or a halfꢀchair with the deviation of
Pd(1) and C(8) atoms by 0.50 and 0.30 Å, respectively,
with the conformation of the second fiveꢀmembered metꢀ
allocycle being changed from a planar to the flattened
envelop with the deviation of Pd(1) atom by 0.25 Å. This
leads to the difference in the geometry of the palladium
atom coordination site: the first molecule has nearly ideal
square planar geometry, whereas the second has a distortꢀ
ed square planar geometry with a slight folding along the
C(11)
Scheme 5
C(12)
C(10)
C(13)
Cl(1)
C(5)
C(9)
C(14)
C(4)
Pd(1)
S(1)
C(1)
C(6)
N(2)
O(1)
C(3)
O(2)
N(1)
C(2)
C(8)
R = C(O)Me (a), OMe (b)
C(7)
i. Catalyst [Pd], DMF, 120 °C, 5 h, K3PO4.
In conclusion, the functionalized mercaptoacetic and
propionic acid amides with an additional Nꢀ or Sꢀdonor cenꢀ
Fig. 5. General view of one of two symmetrically independent
molecules of complex 10 in crystal.

2684
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015
Churusova et al.
Table 2. Catalytic activity of PdII N,N,Sꢀ and S,N,Sꢀcomplexes
in the crossꢀcoupling of 4ꢀbromoacetophenone (11a) with
PhB(OH)2 (Suzuki reaction)
2ꢀ(pyridinꢀ2ꢀyl)ethylamine (0.66 g, 5.41 mmol) and Et3N (0.55 g,
5.41 mmol) in CH2Cl2 (20 mL) at –10 °C under argon atmoꢀ
sphere. The reaction mixture was stirred for 1 h at ~20 °C, then
washed with distilled water. The organic layer was separꢀ
ated, washed with saturated aqueous NaHCO3 and water, dried
over Na2SO4. The solvent was removed in vacuo to give comꢀ
pound 1b (1.01 g, 94%) as a dark oil, which was used further
Catalyst
Yield of product 12a (%)
loading (mol.%)
6a
6b
6c
6d
7
8
10
1
without purification. H NMR (400.13 MHz), δ: 3.09 (t, 2 H,
1
0.1
98
25
95
50
96
37
58
76
87
84
100 100
100 153
3
3
CH2Py, JH,H = 6.2 Hz); 3.78 (dt, 2 H, CH2N, JH,H
=
3
= 6.2 Hz, JH,H = 6.0 Hz); 4.08 (s, 2 H, CH2Cl); 7.24 (d, 1 H,
3
H(C(3)), Py, JH,H = 7.6 Hz); 7.25 (dt, 1 H, H(C(5)), Py,
3JH,H = 3.7 Hz, JH,H = 7.6 Hz); 7.68 (dt, 1 H, H(C(4)), Py,
3
3JH,H = 7.6 Hz, 4JH,H = 1.4 Hz); 7.81 (br.s, 1 H, NH); 8.60 (d, 1 H,
ter in the amine part in the reaction with PdCl2(NCPh)2
easily form κ3ꢀX,N,Sꢀcomplexes (X = N, S) with the triꢀ
dentate monoanionic coordination mode. The prelimiꢀ
nary evaluation of the catalytic activity of the resulting
metal complexes allowed us to determine the main tenꢀ
dencies in the structure—activity correlation, which will
be used for the modification of the ligand framework in
search for new efficient catalysts.
H(C(6)), Py, JH,H = 3.7 Hz). 13C{1H} NMR (100.61 MHz),
3
δ: 36.16 (s, CH2Py); 38.78 (s, CH2N); 42.60 (s, CH2Cl); 121.71
and 123.44 (both s, C(3) and C(5), Py); 136.86 (s, C(4), Py);
148.90 (s, C(6), Py); 158.97 (s, C(2), Py); 165.85 (s, C=O).
Synthesis of 2ꢀphenylsulfanylacetamides 2a—d (general proꢀ
cedure). A solution of thiophenol (0.55 g, 5.00 mmol) in THF
(5 mL) was slowly added dropwise to a stirred suspension of
KOBut (0.56 g, 5.00 mmol) in THF (20 mL) under argon atmoꢀ
sphere. In 30 min, a solution of the corresponding chloroꢀ
acetamide 1a—d (5.00 mmol) in THF (10 mL) was added dropꢀ
wise to the mixture obtained. Then, the reaction mixture was left
under ambient conditions for 12 h and diluted with water, the
product was extracted with chloroform. The organic layer was
separated, washed with saturated aqueous NaHCO3 and water,
dried over Na2SO4. The solvent was removed in vacuo, the residue
was purified by column chromatography on silica gel (eluent
chloroform—methanol (100 : 1)) to give compound 2a (1.14 g,
88%) as a light yellow oil and compounds 2b (1.05 g, 77%), 2c
(1.19 g, 81%), and 2d (1.78 g, 77%) as light yellow (2b) or beige
(2c,d) crystalline solids.
Experimental
1
H, 13C, and 31P NMR spectra were recorded on Bruker
AVꢀ300 (300.13, 75.47, and 121.49 MHz, respectively) and Bruker
AMXꢀ400 (400.13, 100.61, and 161.98 MHz, respectively) in
CDCl3, using residual signals of the solvent as an internal stanꢀ
dard (1H, 13C) and 85% aqueous H3PO4 as an external standard
(31P). 13C NMR spectra were registered in the JMODECHO
mode: the signals of carbon atoms with odd and even numbers of
protons had the opposite polarities. In the description of the
NMR spectra of phenylmercapto derivatives, the numbering
scheme for carbon atoms of the amine component corresponded
to that in the compound names, for neomenthyl analogues the
numbering scheme for carbon atoms is given in Scheme 2. The
notations M and m in the description of NMR spectra of comꢀ
plexes 7 and 8 refer to the major and minor isomer, respectively.
IR spectra were recorded on a MagnaꢀIR 750 Nicolet Fouriꢀ
erꢀtransform spectrometer, resolution 2 cm–1, number of scans
128 (in KBr pellets). Absorption bands were assigned according
to the literature data.12
Reaction progress was monitored by TLC on Silufol TLC
Plates w/UV254. Chromatographic purification of products was
carried out on Macherey—Nagel silica gel (MN Kiselgel 60,
0.063—0.2 mm). Melting points were measured on an EZ Melt
apparatus (Stanford Research Systems, USA) and are uncorꢀ
rected.
Dichloromethane was distilled over P2O5, THF was disꢀ
tilled from Na/benzophenone. NꢀSubstituted chloroacetamides
1a,9a,13 1c,14 and 1d (see Ref. 15) were obtained by the reaction
of ClCH2C(O)Cl with the corresponding amines according to
the known procedures. The synthesis of amide 2b was described
in the patent,16 however, its physicochemical characteristics were
not reported. Neomenthylmercaptane was synthesized accordꢀ
ing to the procedure published earlier.17 Other starting comꢀ
pounds were obtained from commercial sources (Acros, Sigꢀ
ma—Aldrich) and used without additional purification.
2ꢀChloroꢀNꢀ[2ꢀ(pyridinꢀ2ꢀyl)ethyl]acetamide (1b). A soluꢀ
tion of chloroacetyl chloride (0.61 g, 5.41 mmol) in dichloroꢀ
methane (5 mL) was slowly added dropwise to a stirred solution of
2ꢀ(Phenylsulfanyl)ꢀNꢀ(pyridinꢀ2ꢀylmethyl)acetamide (2a).
1H NMR (300.13 MHz), δ: 3.74 (s, 2 H, CH2S); 4.58 (d, 2 H,
CH2Py, 3JH,H = 5.2 Hz); 7.12 (d, 1 H, H(C(3)), Py, 3JH,H = 7.8 Hz);
7.17—7.39 (m, 6 H, 1 H, Py + 5 H, Ph); 7.61 (dt, 1 H, H(C(4)),
Py, 3JH,H = 7.8 Hz, 4JH,H = 1.7 Hz); 7.95 (br.s, 1 H, NH); 8.53
3
(d, 1 H, H(C(6)), Py, JH,H = 4.5 Hz). 13C{1H} NMR (75.47
MHz), δ: 37.62 (s, CH2S); 44.61 (s, CH2Py); 121.64 and 122.22
(both s, C(3) and C(5), Py); 126.58 (s, pꢀC, Ph); 128.64 and
129.06 (both s, oꢀC and mꢀC, Ph); 134.62 (s, ipsoꢀC, Ph); 136.60
(s, C(4), Py); 148.92 (s, C(6), Py); 156.07 (s, C(2), Py); 167.99
(s, C=O). IR, ν/cm–1: 451 w, 475 w, 494 w, 562 w, 613 w, 618 w,
639 w, 690 m, 738 m, 758 m, 993 w, 1024 w, 1047 w, 1088 w,
1149 w, 1162 w, 1227 w, 1319 w, 1354 w, 1418 m, 1438 m, 1475 m,
1482 m, 1546 br, m (NHCO), 1570 m, 1583 m, 1593 m, 1643 s
(C=O), 2856 v.w, 2929 w, 2978 w, 3051 w, 3312 br, m (NH).
Found (%): C, 64.95; H, 5.47; N, 10.69. C14H14N2OS. Calculatꢀ
ed (%): C, 65.09; H, 5.46; N, 10.84.
2ꢀ(Phenylsulfanyl)ꢀNꢀ[2ꢀ(pyridinꢀ2ꢀyl)ethyl]acetamide (2b).
M.p. 75—77 °C (EtOAc). 1H NMR (400.13 MHz), δ: 2.89 (t, 2 H,
3
CH2Py, JH,H = 6.2 Hz); 3.58 (s, 2 H, CH2S); 3.65 (dt, 2 H,
CH2N, 3JH,H = 6.2 Hz, 3JH,H = 6.0 Hz); 6.99 (d, 1 H, H(C(3)),
Py, 3JH,H = 7.7 Hz); 7.06—7.09 (m, 1 H, H(C(5)), Py); 7.12—7.22
3
(m, 5 H, Ph); 7.51 (dt, 1 H, H(C(4)), Py, JH,H = 7.7 Hz,
4JH,H = 1.7 Hz); 7.65 (br.s, 1 H, NH); 8.43 (d, 1 H, H(C(6)), Py,
3JH,H = 4.7 Hz). 13C{1H} NMR (100.61 MHz), δ: 36.54
(s, CH2Py); 37.34 (s, CH2S); 38.67 (s, CH2N); 121.38 and 123.21
(both s, C(3) and C(5), Py); 126.32 (s, pꢀC, Ph); 126.54 and
128.02 (both s, oꢀC and mꢀC, Ph); 134.73 (s, ipsoꢀC, Ph); 136.37

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2685
(s, C(4), Py); 149.02 (s, C(6), Py); 158.95 (s, C(2), Py); 167.63
(s, C=O). IR, ν/cm–1: 448 w, 473 w, 502 w, 558 w, 595 w, 629 w,
690 m, 739 s, 752 w, 775 m, 992 w, 1025 w, 1150 w, 1192 w, 1255 w,
1286 m, 1365 w, 1393 m, 1433 m, 1472 m, 1482 m, 1527 s
(NHCO), 1568 w, 1584 m, 1650 s (C=O), 2865 v.w, 2918 w,
2956 w, 3015 v.w, 3079 v.w, 3330 m (NH). Found (%): N, 10.28;
S, 11.50. C15H16N2OS. Calculated (%): N, 10.29; S, 11.77.
2ꢀPhenylsulfanylꢀNꢀ(quinolinꢀ8ꢀyl)acetamide (2c). M.p.
washed with saturated aqueous NaHCO3 and water, dried over
Na2SO4. The solvent was removed in vacuo, the resulting residue
was purified by column chromatography on silica gel (eluent
EtOAc—hexane (1 : 5) (3), CH2Cl2—hexane (1 : 1) (4)) to give comꢀ
pounds 3 (0.55 g, 45%) and 4 (0.62 g, 50%) as white crystalline solids.
Nꢀ[2ꢀ(Diphenylthiophosphoryl)phenyl]ꢀ2ꢀ(neomenthylsulfanꢀ
20
yl)acetamide (3). M.p. 142—144 °C, [α]D +72.6° (c 0.45,
CHCl3). 31P{1H} NMR (121.49 MHz), δ: 39.71. 1H NMR
(400.13 MHz), δ: 0.81—0.86 (m, 1 H, Alk (Alk is the neomenthyl
substituent)); 0.86 (d, 3 H, H(C(16)), 3JH,H = 6.4 Hz); 0.89 (d, 3 H,
H(C(14)) or H(C(15)), 3JH,H = 6.6 Hz); 0.90 (d, 3 H, H(C(15))
or H(C(14)), 3JH,H = 6.5 Hz); 1.03—1.21 (m, 3 H, Alk); 1.64—1.76
(m, 3 H, Alk); 1.88—1.95 (m, 2 H, Alk); 2.80, 2.82 (ABq, 2 H,
CH2S, JA,B = 15.3 Hz); 3.18 (br.s, H(C(7))); 6.85 (ddd, 1 H,
1
98—100 °C (EtOH). H NMR (400.13 MHz), δ: 3.94 (s, 2 H,
3
CH2S); 7.22 (t, 1 H, pꢀH, Ph, JH,H = 7.2 Hz); 7.29 (t, 2 H,
mꢀH, Ph, 3JH,H = 7.2 Hz); 7.48 (dd, 1 H, H(C(3)), Qu (Qu is the
quinoline substituent), 3JH,H = 8.3 Hz, 3JH,H = 4.3 Hz); 7.54—7.58
(m, 2 H, Ph + 2 H, Qu); 8.17 (dd, 1 H, H(C(4)), Qu, 3JH,H = 8.3 Hz,
4JH,H = 1.5 Hz); 8.77 (dd, 1 H, Qu, 3JH,H = 5.2 Hz, 4JH,H = 1.5 Hz);
3
4
3
3
4
8.87 (dd, 1 H, H(C(2)), Qu, JH,H = 4.3 Hz, JH,H = 1.5 Hz);
11.12 (br.s, 1 H, NH). 13C{1H} NMR (100.61 MHz), δ: 39.87
(s, CH2S); 116.39 (s, C(7), Qu); 121.56 and 121.91 (both s, C(3)
and C(5), Qu); 127.05 and 127.12 (both s, C(6), Qu and pꢀC,
Ph); 127.86 (s, C(4a), Qu); 129.11 and 129.84 (both s, mꢀC and
oꢀC, Ph); 134.02 and 134.44 (both s, C(8), Qu and ipsoꢀC, Ph);
136.10 (s, C(4), Qu); 138.68 (s, C(8a), Qu); 148.36 (s, C(2), Qu);
166.68 (s, C=O). IR, ν/cm–1: 484 m, 539 w, 593 w, 635 w, 688
m, 737 m, 743 m, 760 m, 785 m, 824 m, 881 w, 893 w, 946 w,
1029 w, 1073 w, 1156 m, 1235 w, 1254 w, 1329 m, 1391 m, 1423 m,
1437 m, 1482 m, 1489 m, 1521 and 1530 s (NHCO), 1578 w,
1684 s (C=O), 2910 v.w, 2968 v.w, 3051 v.w, 3079 v.w, 3296 m
(NH). Found (%): C, 69.41; H, 4.82; N, 9.38. C17H14N2OS.
Calculated (%): C, 69.36; H, 4.79; N, 9.52.
H(C(3)), JH,P = 14.4 Hz, JH,H = 7.8 Hz, JH,H = 1.4 Hz);
7.08—7.12 (m, 1 H, Ar); 7.49—7.60 (m, 7 H, Ar); 7.78 (ddd, 4 H,
oꢀH, P(S)Ph2, 3JH,P = 13.7 Hz, 3JH,H = 7.8 Hz, 4JH,H = 1.4 Hz);
3
4
8.00 (dd, 1 H, H(C(6)), JH,H = 8.0 Hz, JH,P = 5.0 Hz); 10.24
(br.s, 1 H, NH). 13C{1H} NMR (100.61 MHz), δ: 20.74, 20.97
(both s, C(14) and C(15)); 22.05 (s, C(16)); 25.71 (s, C(9));
26.25, 29.69 (both s, C(11) and C(13)); 35.23, 35.91 (both s,
C(10) and CH2S); 39.89 (s, C(12)); 45.58, 48.79 (both s, C(7)
1
and C(8)); 123.36 (d, C(2), JC,P = 85.5 Hz); 124.21 (d, C(4),
3JC,P = 12.1 Hz); 125.63 (d, C(6), 2JC,P = 7.3 Hz); 128.63 (d, mꢀC,
P(S)Ph2, 3JC,P = 12.8 Hz); 130.65 (d, ipsoꢀC, P(S)Ph, JP,C
=
1
= 85.8 Hz); 130.80 (d, ipsoꢀC, P(S)Ph, 1JC,P = 85.8 Hz); 131.96
(d, pꢀC, P(S)Ph2, 4JC,P = 2.9 Hz); 132.07 (d, C(3), 2JC,P = 10.3 Hz);
132.12 (d, oꢀC, P(S)Ph, 2JC,P = 11.0 Hz); 132.17 (d, oꢀC, P(S)Ph,
4
Nꢀ[2ꢀ(Diphenylthiophosphoryl)phenyl]ꢀ2ꢀ(phenylsulfanyl)ꢀ
2JC,P = 11.0 Hz); 132.72 (d, C(5), JC,P = 2.2 Hz); 140.73
acetamide (2d). M.p. 118—119 °C. 31P{1H} NMR (161.98 MHz),
(d, C(1), 2JC,P = 4.4 Hz); 168.29 (s, C=O). IR, ν/cm–1: 514 m,
525 m, 537 w, 613 w, 636 m (P=S), 694 m, 717 s, 753 m, 766 w,
1000 w, 1100 m, 1132 w, 1183 w, 1238 w, 1296 m, 1309 w, 1386 w,
1405 w, 1437 s, 1480 w, 1503 s (NHCO), 1575 m, 1689 s (C=O),
2847 w, 2867 w, 2914 m, 2945 m, 3057 w, 3268 br, w (NH).
Found (%): C, 68.95; H, 6.68; N, 2.66. C30H36NOPS2. Calcuꢀ
lated (%): C, 69.06; H, 6.96; N, 2.68.
1
δ: 39.59. H NMR (400.13 MHz), δ: 3.25 (s, 2 H, CH2S); 6.79
3
3
4
(ddd, 1 H, H(C(3)), JH,P = 14.5 Hz, JH,H = 7.8 Hz, JH,H
= 1.4 Hz); 7.03—7.07 (m, 1 H, Ar); 7.15—7.28 (m, 5 H, Ar);
7.43—7.54 (m, 7 H, Ar); 7.73 (ddd, 4 H, oꢀH, P(S)Ph2, 3JP,H
=
=
3
4
= 13.6 Hz, JH,H = 7.8 Hz, JH,H = 1.4 Hz); 7.93 (dd, 1 H,
H(C(6)), 3JH,H = 8.1 Hz, 4JH,P = 5.2 Hz); 10.30 (br.s, 1 H, NH).
13C{1H} NMR (100.61 MHz), δ: 38.44 (s, CH2S); 123.28
Nꢀ[2ꢀ(Diphenylthiophosphoryl)phenyl]ꢀ2ꢀ(neomenthylsulfanꢀ
yl)propionamide (4). M.p. 136—137 °C, [α]D20 +142.54° (c 0.41,
CHCl3). 31P{1H} NMR (121.49 MHz), δ: 40.17. 1H NMR
(400.13 MHz), δ: 0.82—0.98 (m, 10 H, Alk); 1.06—1.22 (m, 3 H,
Alk); 1.56—1.74 (m, 3 H, Alk); 1.87—1.92 (m, 2 H, Alk); 2.21—2.34
(m, 2 H, Alk); 2.39—2.52 (m, 2 H, Alk); 3.08 (br.s, 1 H, H(C(7)));
(d, C(2), 1JC,P = 85.5 Hz); 124.31 (d, C(4), JC,P = 12.0 Hz); 125.55
3
(d, C(6), 3JC,P = 7.1 Hz); 126.51 (s, pꢀC, SPh); 128.60 (d, mꢀC,
P(S)Ph2, 3JC,P = 12.7 Hz); 128.88 and 129.13 (both s, mꢀC and
oꢀC, SPh); 130.54 (d, ipsoꢀC, P(S)Ph2, 1JC,P = 86.2 Hz); 131.95
(s, pꢀC, P(S)Ph2); 132.00 (d, C(3), 2JCP = 9.4 Hz); 132.10 (d, oꢀC,
2
4
3
3
P(S)Ph2, JC,P = 11.1 Hz); 132.67 (d, C(5), JC,P = 2.0 Hz);
134.80 (s, ipsoꢀC, SPh); 140.44 (d, C(1), 2JC,P = 3.8 Hz); 166.85
(s, C=O). IR, ν/cm–1: 509 m, 522 m, 535 w, 613 w, 631 m
(P=S), 653 w, 693 m, 714 s, 740 m, 754 m, 765 w, 898 w, 999 w,
1025 w, 1072 w, 1101 m, 1130 w, 1184 w, 1223 w, 1248 w, 1292 m,
1312 w, 1403 w, 1438 s, 1482 m, 1504 s (NHCO), 1572 m, 1588
w, 1683 s (C=O), 2975 w, 3059 w, 3201 w (NH). Found (%):
C, 67.09; H, 4.40; N, 2.94. C26H22NOPS2•0.2 H2O. Calculatꢀ
ed (%): C, 67.42; H, 4.87; N, 3.02.
6.83 (ddd, 1 H, H(C(3)), JH,P = 14.5 Hz, JH,H = 7.6 Hz,
4JH,H = 1.4 Hz); 7.09—7.14 (m, 1 H, Ar); 7.51—7.65 (m, 7 H, Ar);
7.77 (ddd, 4 H, oꢀH, P(S)Ph2, 3JH,P = 13.7 Hz, 3JH,H = 8.7 Hz,
4JH,H = 1.6 Hz); 8.13 (dd, 1 H, H(C(6)), 3JH,H = 7.6 Hz, 4JH,P
=
= 4.9 Hz); 10.00 (br.s, 1 H, NH). 13C{1H} NMR (100.61 MHz),
δ: 20.74, 20.99 (both s, C(14) and C(15)); 22.13 (s, C(16)); 25.87
(s, C(9)); 26.22 (s, C(11) or C(13)); 26.59 (s, CH2S); 29.83
(s, C(13) or C(11)); 35.29 (s, C(10)); 37.91 (s, CH2); 40.50
(s, C(12)); 46.81, 48.74 (both s, C(7) and C(8)); 121.93 (d, C(2),
3
Synthesis of 2ꢀneomenthylsulfanylacetamides 3 and 4 (generꢀ
al procedure). A solution of (1S,2S,5R)ꢀ2ꢀisopropylꢀ5ꢀmethylꢀ
cyclohexanethiol (neomenthylmercaptane) (0.40 g, 2.33 mmol)
in THF (5 mL) was slowly added dropwise to a stirred suspension
of KOBut (0.26 g, 2.33 mmol) in THF (15 mL) under argon
atmosphere. In 30 min, a solution of chloroacetamide 1d
or 5 (2.33 mmol) in THF (10 mL) was added dropwise to the
mixture obtained. Then, the reaction mixture was left under
ambient conditions for 12 h and diluted with water, the product was
extracted with chloroform. The organic layer was separated,
1JC,P =85.5 Hz); 123.98 (d, C(4), JC,P = 12.5 Hz); 125.24
3
3
(d, C(6), JP,C = 7.0 Hz); 128.72 (d, mꢀC, P(S)Ph2, JC,P
=
= 12.8 Hz); 130.63 (d, ipsoꢀC, P(S)Ph, 1JC,P = 85.8 Hz); 130.64
(d, ipsoꢀC, P(S)Ph, JC,P = 86.2 Hz); 132.03—132.23 (m, overꢀ
1
lapped signals of oꢀC and pꢀC, P(S)Ph2 and C(3)); 132.86 (d,
4
2
C(5), JC,P = 2.2 Hz); 140.95 (d, C(1), JC,P = 4.4 Hz); 169.35
(s, C=O). IR, ν/cm–1: 504 w, 516 m, 531 w, 614 w, 635 m
(P=S), 693 m, 716 s, 757 m, 999 w, 1101 m, 1130 w, 1161 w,
1183 w, 1234 w, 1293 m, 1365 w, 1436 s, 1456 w, 1480 w, 1503 m
(NHCO), 1573 m, 1594 w, 1691 and 1702 m (C=O), 2837 w,

2686
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015
Churusova et al.
2867 w, 2913 m, 2949 m, 3053 w, 3283 br, w (NH). Found (%):
C, 69.74; H, 7.26; N, 2.62. C31H38NOPS2. Calculated (%):
C, 69.50; H, 7.15; N, 2.61.
and 122.89 (both s, C(3) and C(5), Py); 129.97 (s, oꢀC or mꢀC,
Ph); 130.44 (s, pꢀC, Ph); 130.81 (s, ipsoꢀC, Ph); 130.94 (s, oꢀC
or mꢀC, Ph); 139.07 (s, C(4), Py); 148.60 (s, C(6), Py); 167.53
(s, C(2), Py); 175.98 (s, C=O). IR, ν/cm–1: 439 w, 476 w, 687 w,
711 w, 749 m, 763 m, 889 w, 1000 w, 1052 w, 1095 w, 1159 w,
1212 w, 1281 w, 1384 m, 1442 m, 1483 m, 1563 m, 1596 s, 1614 sh,
s, 1618 s (C=O), 2093 w, 3075 w. Found (%): N, 6.84; S, 7.72.
C14H13ClN2OPdS. Calculated (%): N, 7.02; S, 8.03.
3ꢀChloroꢀNꢀ[2ꢀ(diphenylthiophosphoryl)phenyl]propionꢀ
amide (5). A solution of 3ꢀchloropropionyl chloride (0.51 g,
4.01 mmol) in dichloromethane (5 mL) was slowly added dropꢀ
wise to a mixture of 2ꢀdiphenylthiophosphorylaniline (1.24 g,
4.01 mmol) and Et3N (0.41 g, 4.06 mmol) in CH2Cl2 (40 mL) at
5—10 °C. The reaction mixture was stirred for 4 h at ~20 °C,
then washed with water. The organic layer was separated and
dried over Na2SO4. The solvent was removed in vacuo, the resiꢀ
due was purified by column chromatography on silica gel (eluent
EtOAc—hexane (1 : 3)) to give compound 5 (1.00 g, 63%) as
a white crystalline solid, m.p. 159—160 °C. 31P{1H} NMR (121.49
3
κ ꢀN,N,SꢀChloro[Nꢀ(2ꢀphenylsulfanylacetyl)ꢀNꢀ(2ꢀpyridinꢀ
2ꢀylethyl)amido]palladium(II) (6b). M.p. 230—232 °C (decomp.).
1H NMR (400.13 MHz), δ: 2.86—2.93 (m, 1 H, CH2Py); 3.10—3.13
(m, 2 H, CH2N); 3.50—3.55 (m, 1 H, CH2Py); 3.60 (d, 1 H,
CH2S, 2JH,H = 16.7 Hz); 3.94 (d, 1 H, CH2S, 2JH,H = 16.7 Hz);
7.30 (m, 1 H, H(C(5)), Py); 7.35 (d, 1 H, H(C(3)), Py, 3JH,H
=
1
MHz), δ: 40.28. H NMR (300.13 MHz), δ: 2.49 (t, 2 H, CH2,
= 7.7 Hz); 7.42—7.47 (m, 3 H, mꢀC, Ph and H(C(4)), Py); 7.82
(dt, 1 H, pꢀH, Ph, 3JH,H = 7.7 Hz, 4JH,H = 1.5 Hz); 7.88 (dd, 2 H,
oꢀH, Ph, 3JH,H = 7.6 Hz, 4JH,H = 1.5 Hz); 9.17 (dd, 1 H, H(C(6)),
3JH,H = 6.9 Hz); 3.54 (t, 2 H, CH2Cl, 3JH,H = 6.9 Hz); 6.81 (dd,
1 H, H(C(3)), Ar, 3JH,P = 14.5 Hz, 3JH,H = 7.8 Hz); 7.06—7.11,
7.47—7.61 (both m, 1 H + 7 H, Ar); 7.72 (dd, 4 H, oꢀH, Ph,
3
4
Py, JH,H = 5.9 Hz, JH,H = 1.5 Hz). 13C{1H} NMR (75.47
MHz), δ: 41.09, 41.15, and 42.40 (three s, CH2S, CH2Py and
CH2N); 122.80 and 124.62 (both s, C(3) and C(5), Py); 129.92
(s, oꢀC or mꢀC, Ph); 130.37 (s, pꢀC, Ph); 130.41 (s, oꢀC or mꢀC,
Ph); 130.57 (s, ipsoꢀC, Ph); 139.75 (s, C(4), Py); 152.92 (s, C(6),
Py); 159.07 (s, C(2), Py); 178.10 (s, C=O). IR, ν/cm–1: 433 w,
501 w, 527 w, 587 w, 658 w, 697 w, 759 m, 768 m, 788 w, 898 w,
938 w, 1023 w, 1112 w, 1156 m, 1228 w, 1239 w, 1252 w, 1306 w,
1333 w, 1386 m, 1438 m, 1480 m, 1572 m, 1595 s (C=O), 2856
w, 2921 w, 2998 w. Found (%): C, 43.69; H, 3.77; N, 6.65.
C15H15ClN2OPdS. Calculated (%): C, 43.60; H, 3.66; N, 6.78.
3
3JH,P = 13.9 Hz, JH,H = 7.1 Hz); 8.14 (dd, 1 H, H(C(6)), Ar,
3JH,H = 8.1 Hz, 4JH,P = 5.1 Hz); 10.21 (s, 1 H, NH). IR, ν/cm–1
:
503 w, 516 s, 527 w, 551 w, 614 w, 637 m (P=S), 672 w, 696 s,
714 s, 757 s, 997 w, 1073 w, 1098 m, 1132 w, 1189 w, 1236 w,
1300 m, 1438 s, 1481 w, 1508 s (NHCO), 1571 m, 1593 w, 1687 s
(C=O), 3049 w, 3274 m (NH). Found (%): C, 63.09; H, 4.94;
N, 3.44. C21H19ClNOPS. Calculated (%): C, 63.08; H, 4.79;
N 3.50. The side product Nꢀ[2ꢀ(diphenylthiophosphoryl)phenyl]ꢀ
propꢀ2ꢀenamide (0.30 g, 21%) was isolated as a white crystalline
compound, m.p. 156—157 °C. 31P{1H} NMR (121.49 MHz),
1
3
δ: 40.28. H NMR (300.13 MHz), δ: 5.60 (X, ABX, 1 H, CH2,
κ ꢀN,N,SꢀChloro[Nꢀ(2ꢀphenylsulfanylacetyl)ꢀNꢀ(quinolinꢀ8ꢀ
JB,X =10.6 Hz, JA,X = 0.7 Hz); 6.02 (B, ABX, 1 H, CH, JA,B
=
yl)amido]palladium(II) (6c). M.p. 215—217 °C (decomp.). 1H NMR
(400.13 MHz), δ: 3.93 (d, 1 H, CH2S, 2JH,H = 17.1 Hz); 4.54 (d,
1 H, CH2S, 2JH,H = 17.1 Hz); 7.37—7.52 (m, 6 H, Ar); 7.98—8.01
= 17.1 Hz, JB,X = 10.6 Hz); 6.20 (A, ABX, 1 H, CH2, JA,B = 17.1 Hz,
3
JA,X = 0.7 Hz); 6.81 (ddd, 1 H, H(C(3)), JH,P = 14.5 Hz,
3JH,H = 7.9 Hz, 4JH,H = 1.4 Hz); 7.05—7.10 (m, 1 H, Ar); 7.46—7.60
(m, 2 H, Ar), 8.25 (dd, 1 H, H(C(4)), Qu, JH,H = 8.3 Hz,
3
3
(m, 8 H, Ar); 7.72 (ddd, 4 H, oꢀH, P(S)Ph2, JH,P = 13.7 Hz,
4JH,H = 1.5 Hz); 8.90 (dd, 1 H, Qu, 3JH,H = 8.0 Hz, 4JH,H = 1.0 Hz);
3JH,H = 7.6 Hz, 4JH,H = 1.5 Hz); 8.28 (dd, 1 H, H(C(6)), 3JH,H
=
9.00 (dd, 1 H, H(C(2)), Qu, JH,H = 5.2 Hz, JH,H = 1.5 Hz).
13C{1H} NMR (100.61 MHz), δ: 46.58 (s, CH2S); 120.93, 121.09
and 122.06 (three s, C(3), C(5) and C(7), Qu); 129.29 (s, pꢀC,
Ph or C(6), Qu); 129.76 (s, C(4a), Qu); 130.04 (s, mꢀC or oꢀC,
Ph); 130.45 (s, C(6), Qu or pꢀC, Ph); 130.92 (s, oꢀC or mꢀC, Ph);
139.23 (s, C(4), Qu); 145.80, 146.80 (both s, C(8) and C(8a),
Qu); 148.63(s, C(2), Qu); 175.81 (s, C=O).* IR spectrum,
ν/cm–1: 469 w, 499 w, 540 w, 688 w, 746 m, 755 w, 766 w, 780 w,
826 m, 895 w, 984 w, 999 w, 1100 w, 1173 w, 1233 w, 1339 m,
1385 m, 1443 w, 1464 m, 1483 w, 1505 m, 1571 w, 1618 s (C=O),
2899 w, 2998 v.w, 3057 v.w. Found (%): C, 46.83; H, 3.03; N, 6.59.
C17H13ClN2OPdS. Calculated (%): C, 46.91; H, 3.01; N, 6.44.
3
4
= 8.2 Hz, 4JH,P = 5.2 Hz); 10.28 (s, 1 H, NH). IR, ν/cm–1: 505
w, 518 m, 614 w, 635 m (P=S), 676 w, 693 m, 712 s, 753 m, 775
w, 798 w, 976 m, 998 w, 1077 w, 1100 m, 1131 w, 1178 m, 1283
m, 1311 w, 1402 w, 1435 s, 1480 w, 1505 s (NHCO), 1575 m,
1595 w, 1629 w, 1685 s (C=O), 3055 w, 3284 w (NH). Found (%):
C, 69.41; H, 5.06; N, 3.69. C21H18NOPS. Calculated (%):
C, 69.40; H, 4.99; N, 3.85.
3
Synthesis of palladium κ ꢀN,N,Sꢀcomplexes 6a—c (general
procedure). A solution of PdCl2(NCPh)2 (76 mg, 0.198 mmol) in
dichloromethane (5 mL) was slowly added dropwise to a soluꢀ
tion of the corresponding ligand 2a—c (0.198 mmol) and Et3N
(28 μL, 0.200 mmol) in CH2Cl2 (10 mL). In 12 h, the solvent
was removed in vacuo, the residue was purified by column chroꢀ
matography on silica gel (eluent CH2Cl2—MeOH (50 : 1))
to give complexes 6a (70 mg, 89%), 6b (60 mg, 73%), and
6c (80 mg, 93%) as yellow (6a,b) or dark orange (6c) crystalꢀ
line solids.
3
Synthesis of palladium κ ꢀS,N,Sꢀcomplexes 6d, 7, and 8
(general procedure). A solution of PdCl2(NCPh)2 (64 mg,
0.167 mmol) in dichloromethane (5 mL) was slowly added dropꢀ
wise to a solution of ligand 2d, 3, or 4 (0.167 mmol) in CH2Cl2
(5 mL). In 12 h, the solvent was removed in vacuo, the residue
was purified by column chromatography on silica gel (eluent
CH2Cl2—MeOH (50 : 1)) to give complexes 6d (90 mg, 90%),
7 (93 mg, 82%), and 8 (101 mg, 89%) as red (6d) or orange (7, 8)
crystalline solids.
3
κ ꢀN,N,SꢀChloro[Nꢀ(2ꢀphenylsulfanylacetyl)ꢀNꢀ(pyridinꢀ2ꢀ
ylmethyl)amido]palladium(II) (6a). M.p. 225—227 °C (decomp.).
1H NMR (400.13 MHz), δ: 3.72 (d, 1 H, CH2S, 2JH,H = 16.8 Hz);
2
3
4.16 (d, 1 H, CH2S, JH,H = 16.8 Hz); 4.88 (s, 2 H, CH2Py);
κ ꢀS,N,SꢀChloro{Nꢀ[2ꢀ(diphenylthiophosphoryl)phenyl]ꢀNꢀ
7.32 (m, 1 H, H(C(5)), Py); 7.37 (d, 1 H, H(C(3)), Py, 3JH,H
=
(2ꢀphenylsulfanylacetyl)amido}palladium(II) (6d). M.p. >253 °C
1
= 8.0 Hz); 7.43—7.47 (m, 3 H, Ar); 7.86 (dt, 1 H, pꢀH, Ph,
(decomp.). 31P{1H} NMR (161.98 MHz), δ: 37.98. H NMR
4
3JH,H = 7.7 Hz, JH,H = 1.5 Hz); 7.93—7.95 (m, 2 H, Ar); 8.89
(dd, 1 H, H(C(6)), Py, 3JH,H = 5.8 Hz, 4JH,H = 0.9 Hz). 13C{1H}
NMR (75.47 MHz), δ: 45.19 (s, CH2S); 56.02 (s, CH2Py); 121.55
* The signal of the ipsoꢀC quaternary carbon atom of the phenyl
group was not observed.

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2687
(400.13 MHz), δ: 3.51, 3,56 (ABq, 2 H, CH2S, JA,B = 16.2 Hz);
1624 s (C=O), 2866 m, 2921 m, 2949 m, 3057 w. Found (%):
C, 53.46; H, 5.24; N, 2.03. C30H35ClNOPPdS2•0.2CH2Cl2. Calꢀ
culated (%): C, 53.38; H, 5.25; N, 2.06.
3
6.77 (dd, 1 H, H(C(3)), 3JH,P = 14.8 Hz, JH,H = 7.6 Hz); 7.01
(dt, 1 H, H(C(4)), 3JH,H = 7.6 Hz, 4JH,P = 2.7 Hz); 7.16 (dd, 1 H,
3
4
3
H(C(6)), JH,H = 7.6 Hz, JH,P = 5.9 Hz); 7.43—7.49 (m, 4 H,
Ar); 7.57—7.62 (m, 4 H, Ar); 7.66—7.71 (m, 4 H, Ar); 7.85—7.94
(m, 4 H, Ar). 13C{1H} NMR (100.61 MHz), δ: 42.88 (s, CH2S);
122.60 (d, C(2), 1JC,P = 86.2 Hz); 123.70 (d, C(4), 3JC,P = 13.2 Hz);
κ ꢀS,N,SꢀChloro{Nꢀ[2ꢀ(diphenylthiophosphoryl)phenyl]ꢀNꢀ
(2ꢀneomenthylsulfanylpropyl)amido}palladium(II) (8). The ratio
of m and M isomers was 1 : 3. M.p. >220 °C (decomp.). 31P{1H}
NMR (121.49 MHz), δ: 36.81 (m), 36.96 (M). 1H NMR
(400.13 MHz), δ: 0.80 (d, 3 H, H(C(16)) (M), 3JH,H = 6.4 Hz);
0.83—0.88 (m, 1 H (M) + 1 H (m), Alk); 0.89 (d, 3 H, H(C(16))
(m), 3JH,H = 6.9 Hz); 0.91 (d, 3 H, H(C(14)) or H(C(15)) (m),
3JH,H = 7.1 Hz); 0.94 (d, 3 H, H(C(14)) or H(C(15)) (M),
3JH,H = 6.5 Hz); 1.00 (d, 3 H, H(C(15)) or H(C(14)) (M),
3JH,H = 6.2 Hz); 1.06 (d, 3 H, H(C(15)) or H(C(14)) (m),
3JH,H = 6.6 Hz); 1.26—1.87 (m, 7 H (M) + 7 H (m), Alk); 2.10—2.19
(m, 1 H (M) + 1 H (m), Alk); 2.29—2.43 (m, 1 H (M) + 1 H (m),
Alk); 2.62—3.04 (m, 3 H (M) + 3 H (m), Alk); 3.58 (br.s, 1 H,
1
124.54 (d, ipsoꢀC, Ph, JC,P = 86.2 Hz); 128.13 (d, ipsoꢀC, Ph,
3
1JC,P = 88.8 Hz); 129.11 (d, mꢀC, P(S)Ph, JC,P = 13.6 Hz);
3
129.22 (d, mꢀC, P(S)Ph, JC,P = 12.8 Hz); 129.68 (s, ipsoꢀC,
SPh); 129.80 (s, mꢀC or oꢀC, SPh); 129.84 (d, C(6), 3JC,P = 8.0 Hz);
130.09 (s, pꢀC, SPh); 130.64 (s, oꢀC or mꢀC, SPh); 130.89
(d, C(3), 2JC,P = 9.2 Hz); 132.08 (d, oꢀC, P(S)Ph, 2JC,P = 11.7 Hz);
132.92 (d, pꢀC, P(S)Ph or C(5), 4JC,P = 2.9 Hz); 133.22 (d, oꢀC,
2
P(S)Ph, JC,P = 10.6 Hz); 133.41 (d, pꢀC, P(S)Ph or C(5),
4JP,C=2.6 Hz); 133.51 (d, pꢀC, P(S)Ph or C(5), 4JC,P = 2.2 Hz);
2
150.47 (d, C(1), JC,P = 3.3 Hz); 176.70 (s, C=O). IR, ν/cm–1
494 w, 523 m, 532 m, 604 m (P=S), 621 w, 659 w, 690 m, 704 m,
723 w, 740 m, 753 m, 906 w, 999 w, 1025 w, 1070 w, 1105 m,
1136 w, 1162 w, 1186 w, 1266 w, 1309 m, 1436 m, 1463 m, 1481 w,
1565 w, 1578 m, 1624 s (C=O), 2919 w, 2973 w, 3055 w. Found (%):
C, 52.30; H, 3.53; N, 2.30. C26H21ClNOPPdS2. Calculated (%):
C, 52.01; H, 3.53; N, 2.33.
:
H(C(7)) (M)); 3.80 (br.s, 1 H, H(C(7)) (m)); 6.87 (dd, 1 H,
3
3
H(C(3)) (m), JH,P = 14.7 Hz, JH,H = 7.6 Hz); 6.89 (dd, 1 H,
3
3
H(C(3)) (M), JH,P = 14.8 Hz, JH,H = 7.6 Hz); 7.09 (dt, 1 H,
3
4
H(C(4)) (m), JH,H = 7.6 Hz, JH,P = 3.0 Hz); 7.10 (dt, 1 H,
3
4
H(C(4)) (M), JH,H = 7.6 Hz, JH,P = 3.2 Hz); 7.27 (dd, 1 H,
3
4
H(C(6)) (m), JH,H = 8.0 Hz, JH,P = 5.4 Hz); 7.32 (dd, 1 H,
3
4
H(C(6)) (M), JH,H = 7.8 Hz, JH,P = 5.5 Hz); 7.50—7.62 (m,
6 H (M) + 6 H (m), Ar); 7.67—7.74 (m, 3 H (M) + 3 H (m), Ar);
7.79 (dd, 2 H, oꢀH, P(S)Ph (m), 3JH,P = 14.3 Hz, 3JH,H = 7.2 Hz);
3
κ ꢀS,N,SꢀChloro{Nꢀ[2ꢀ(diphenylthiophosphoryl)phenyl]ꢀNꢀ
(2ꢀneomenthylsulfanylacetyl)amido}palladium(II) (7). The ratio of M
and m isomers was 2 : 1. M.p. >270 °C (decomp.). 31P{1H} NMR
7.81 (dd, 2 H, oꢀH, P(S)Ph (M), JH,P = 14.5 Hz, JH,H
=
3
3
1
(121.49 MHz), δ: 37.89. H NMR (400.13 MHz), δ: 0.90—0.92
= 7.4 Hz). 13C{1H} NMR (100.61 MHz), δ: 20.30 (s, C(16)
(M)); 21.25 (s, C(16) (m)); 21.96 (s, C(14) or C(15) (M + m));
22.10 (s, C(15) or C(14) (M)); 22.12 (s, C(15) or C(14) (m));
24.41 (s, C(9) (M)); 24.58 (s, C(9) (m)); 26.50 (s, C(11) or C(13)
(m)); 27.13 (s, CH2S (m)); 27.22 (s, C(11) or C(13) (M)); 28.73
(s, C(13) or C(11) (m)); 29.79 (s, C(11) or C(13) (M)); 33.17
(s, CH2S (M)); 34.91 (s, C(10) (M)); 35.10 (s, C(10) (m)); 38.88
(s, CH2 (m)); 41.83 (s, C(12) (m)); 42.12 (s, CH2 (M)); 43.04
(s, C(12) (M)); 49.15 (s, C(7) or C(8) (M)); 49.89 (s, C(8) or C(7)
(m)); 52.57 (s, C(7) or C(8) (m)); 57.23 (s, C(8) or C(7) (M));
(m, 3 H (M) + 3 H (m), H(C(16))); 0.95 (d, 3 H, H(C(14)) or
3
H(C(15)) (M), JH,H = 6.4 Hz); 0.96 (d, 3 H, H(C(14)) or
3
H(C(15)) (m), JH,H = 6.2 Hz); 0.99 (d, 3 H, H(C(15)) or
3
H(C(14)) (M), JH,H = 6.5 Hz); 1.28 (d, 3 H, H(C(15)) or
H(C(14)) (m), 3JH,H = 6.4 Hz); 1.52—1.64, 1.79—1.88 (both m,
7 H (M) + 7 H (m), Alk); 2.19—2.22 (m, 1 H (m), Alk); 2.55—2.66
(m, 1 H (M) + 1 H (m), Alk); 2.88—2.91 (m, 1 H (M), Alk); 3.04
2
(d, 1 H, CH2S (m), JH,H = 16.0 Hz); 3.06 (d, 1 H, CH2S (M),
2
2JH,H = 16.0 Hz); 3.32 (d, 1 H, CH2S (m), JH,H = 16.0 Hz);
2
3
3.34 (d, 1 H, CH2S (M), JH,H = 16.0 Hz); 3.62 (br.s, 1 H,
123.62 (d, C(4) (m), JC,P = 11.7 Hz); 123.75 (d, C(4) (M),
H(C(7)) (M)); 3.86 (br.s, 1 H, H(C(7)) (m)); 6.81 (dd, 1 H,
H(C(3)), 3JH,P = 14.7 Hz, 3JH,H = 7.9 Hz); 7.04—7.08, 7.45—7.72
3JC,P = 13.2 Hz); 124.24 (d, C(2) (M), 1JC,P = 85.8 Hz); 124.30
1
(d, C(2) (m), JC,P = 85.1 Hz); 125.83 (d, ipsoꢀC, P(S)Ph (m),
3
(both m, 1 H + 10 H, Ar); 7.87 (dd, 2 H, oꢀH, P(S)Ph, JH,P
=
1JC,P = 87.3 Hz); 125.93 (d, ipsoꢀC, P(S)Ph (M), 1JC,P = 86.9 Hz);
126.99 (d, ipsoꢀC, P(S)Ph (M), 1JC,P = 89.5 Hz); 127.11 (d, ipsoꢀC,
= 14.7 Hz, JH,H = 7.3 Hz). 13C{1H} NMR (75.47 MHz), δ:
20.67 (s, C(14) or C(15) (M)); 21.35 (s, C(16) (M + m)); 21.79
(s, C(14) or C(15) (m)); 22.04 (s, C(15) or C(14) (M + m));
25.22 (s, C(9) (M + m)); 26.30 (s, C(11) or C(13) (m)); 27.22
(s, C(11) or C(13) (M)); 28.91 (s, C(13) or C(11) (m)); 29.84
(s, C(11) or C(13) (M)); 34.80 (s, CH2S (M)); 35.19 (s, CH2S (m));
38.04, 38.18 (both s, C(10) and C(12) (m)); 42.58, 42.91 (both s,
C(10) and C(12) (M)); 49.14 (s, C(7) or C(8) (M)); 49.46, 51.86
(both s, C(8) and C(7) (m)); 55.65 (s, C(7) or C(8) (M)); 123.71
3
P(S)Ph (m), 1JC,P = 89.5 Hz); 128.77 (d, mꢀC, P(S)Ph (M + m),
3
3JC,P = 13.6 Hz); 129.13 (d, mꢀC, P(S)Ph (M + m), JC,P
=
3
= 12.5 Hz); 130.56 (d, C(6) (M), JC,P = 8.1 Hz); 130.90
(d, C(6) (m), 3JC,P = 8.1 Hz); 131.50 (d, C(3) (M), 2JC,P = 9.5 Hz);
131.60 (d, C(3) (m), JC,P = 11.0 Hz); 131.82 (d, oꢀC, P(S)Ph
2
(m), 2JC,P = 11.4 Hz); 131.85 (d, oꢀC, P(S)Ph (M), 2JC,P = 11.7 Hz);
132.70 (d, pꢀC, P(S)Ph (M + m), 4JC,P = 3.3 Hz); 133.30 (d, pꢀC,
P(S)Ph (M + m), 4JC,P = 2.6 Hz); 133.46 (d, oꢀC, P(S)Ph (m),
3
3
4
(d, C(4), JC,P = 13.2 Hz); 129.04 (d, mꢀC, P(S)Ph, JC,P
=
2JC,P = 10.3 Hz); 133.47 (d, C(5) (m), JC,P = 2.6 Hz); 133.49
3
2
= 13.2 Hz); 129.21 (d, mꢀC, P(S)Ph, JC,P = 12.1 Hz); 129.73
(d, C(6), JC,P = 7.7 Hz); 131.11 (d, C(3), JC,P = 9.3 Hz);
131.98 (d, oꢀC, P(S)Ph, JC,P = 11.0 Hz); 132.77 (s, pꢀC,
(d, oꢀC, P(S)Ph (M), JC,P = 10.3 Hz); 133.57 (d, C(5) (M),
3
2
2
4JC,P = 2.2 Hz); 150.45 (d, C(1) (m), JC,P = 4.8 Hz); 150.49
2
2
(d, C(1) (M), JC,P = 3.7 Hz); 172.13 (s, C=O (M)); 172.18
P(S)Ph); 132.28—133.53 (overlapped signals of C(5), oꢀC, and
pꢀC, P(S)Ph); 150.47 (s, C(1)); 176.88 (s, C=O (m)); 177.40
(s, C=O (M)).* IR, ν/cm–1: 524 m, 536 m, 601 m (P=S), 622 w,
691 m, 705 m, 720 w, 741 m, 756 m, 999 w, 1107 m, 1139 w, 1187 w,
1267 w, 1330 m, 1388 w, 1438 m, 1462 m, 1482 w, 1561 w, 1580 m,
(s, C=O (m)). IR, ν/cm–1: 499 w, 525 m, 541 w, 599 m (P=S), 620
w, 691 m, 702 m, 719 m, 752 w, 998 w, 1106 m, 1135 w, 1185 w,
1265 w, 1301 w, 1369 m, 1437 s, 1461 m, 1579 m, 1606 s (C=O),
2864 m, 2920 m, 2947 m, 3054 w. Found (%): C, 55.19; H, 5.51;
N, 2.06. C31H37ClNOPPdS2. Calculated (%): C, 55.03; H, 5.51;
N. 2.07.
* The signals of the C(2) and ipsoꢀC quaternary carbon atoms of
the diphenylthiophosphotyl group were not observed.
2ꢀPhenylsulfinylꢀNꢀ(pyridinꢀ2ꢀylmethyl)acetamide (9). A 7%
solution of hydrogen peroxide (5.67 g) in tertꢀbutyl alcohol was

2688
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015
Churusova et al.
slowly added dropwise to a solution of compound 2a (0.43 g,
1.67 mmol) in methanol (15 mL). The reaction mixture was
stirred for 12 h at ~20 °C and then diluted with distilled water
(30 mL), the product was extracted with chloroform. The organꢀ
ic layer was separated and dried over Na2SO4. The solvent was
removed in vacuo. The residue was purified by column chromatoꢀ
graphy on silica gel (eluent CHCl3—MeOH (50 : 1)) to give
compound 9 (0.29 g, 63%) as a yellow oil. 1H NMR
(400.13 MHz), δ: 3.67 (d, 1 H, CH2S(O), 2JH,H = 13.9 Hz); 3.77
and Et3N (36 μL, 0.258 mmol) in CH2Cl2 (10 mL). In 12 h, the
solvent was removed in vacuo, the residue was purified by colꢀ
umn chromatography on silica gel (eluent CH2Cl2—MeOH
(50 : 1)) to give complex 10 (101 mg, 95%) as a light yelꢀ
1
low crystalline solid. M.p. 215—220 °C (decomp.). H NMR
(400.13 MHz), δ: 4.48 (d, 1 H, CH2S(O), 2JH,H = 16.7 Hz); 4.71
2
(d, 1 H, CH2S(O), JH,H = 16.7 Hz); 5.01, 5.11 (ABq, 2 H,
CH2Py, JA,B = 20.3 Hz); 7.41 (t, 1 H, H(C(5)), Py, 3JH,H = 6.5 Hz);
7.49 (d, 1 H, H(C(3)), Py, 3JH,H = 8.0 Hz); 7.65—7.74 (m, 3 H,
mꢀH, Ph and H(C(4)), Py); 7.96 (dt, 1 H, pꢀH, Ph, 3JH,H = 7.8 Hz,
2
(d, 1 H, CH2S(O), JH,H = 13.9 Hz); 4.52 (d, 2 H, CH2Py,
3JH,H = 5.4 Hz); 7.17—7.20 (m, 2 H, Py); 7.45—7.48 (m, 3 H, Ph);
7.60—7.65 (m, 1 H, Py + 2 H, Ph); 7.93 (br.s, 1 H, NH); 8.52
(d, 1 H, H(C(6)), Py, 3JH,H = 4.5 Hz). 13C{1H} NMR (75.47 MHz),
δ: 44.67 (s, CH2Py); 60.10 (s, CH2S(O)); 121.73 and 122.20
(both s, C(3) and C(5), Py); 123.84 and 129.15 (both s, oꢀC and
mꢀC, Ph); 131.27 (s, pꢀC, Ph); 136.64 (s, C(4), Py); 141.85
(s, ipsoꢀC, Ph); 148.85 (s, C(6), Py); 155.90 (s, C(2), Py); 163.57
(s, C=O). IR, ν/cm–1: 490 w, 612 w, 632 w, 691 m, 749 m, 892 w,
998 w, 1021 m, 1043 m (S=O), 1072 w, 1087 m, 1149 w, 1201 w,
1254 w, 1310 m, 1443 m, 1476 m, 1551 br, m (NHCO), 1571 m,
1592 m, 1664 sh, s, 1669 s (C=O), 2924 w, 3057 m, 3278 br,
m (NH). Found (%): C, 60.98; H, 5.33; N, 9.79. C14H14N2O2S.
Calculated (%): C, 61.29; H, 5.14; N, 10.21.
4JH,H = 1.6 Hz); 8.22 (dd, 2 H, oꢀH, Ph, 3JH,H = 8.1 Hz, 4JH,H
=
3
= 1.6 Hz); 8.92 (dd, 1 H, H(C(6)), Py, JH,H = 5.3 Hz,
4JH,H = 0.7 Hz). 13C{1H} NMR (100.61 MHz), δ: 56.92
(s, CH2Py); 70.48 (s, CH2S(O)); 121.79 and 123.29 (both s, C(3)
and C(5), Py); 125.43 and 129.98 (both s, oꢀC and mꢀC, Ph);
133.84 (s, pꢀC, Ph); 139.88 (s, C(4), Py); 141.20 (s, ipsoꢀC, Ph);
148.96 (s, C(6), Py); 167.31 (s, C(2), Py); 169.34 (s, C=O). IR,
ν/cm–1: 420 w, 470 w, 508 m, 531 m, 683 m, 713 w, 750 m,
765 m, 879 w, 998 w, 1033 w, 1080 m, 1096 m, 1117 m (S=O),
1153 m, 1218 m, 1286 w, 1369 m, 1392 m, 1445 m, 1486 m,
1566 m, 1600 sh, s, 1626 s (C=O), 2914 w, 2981 w, 3051 w.
Found (%): C, 40.54; H, 3.37; N, 6.77. C14H13ClN2O2PdS. Calꢀ
culated (%): C, 40.50; H, 3.16; N, 6.75.
3
κ ꢀN,N,SꢀChloro[Nꢀ(pyridinꢀ2ꢀylmethyl)ꢀNꢀ(2ꢀphenylsulfꢀ
Catalytic studies. A Schlenk testꢀtube was charged with aryl
bromide 11a,b (0.125 mmol), PhB(OH)2 (23 mg, 0.188 mmol),
DMF (0.5 mL), and freshly powdered K3PO4 (53 mg, 0.25 mmol),
then a calculated amount of the catalyst as a 0.1 M solution in
inylacetyl)amido]palladium(II) (10). A solution of PdCl2(NCPh)2
(98 mg, 0.255 mmol) in dichloromethane (5 mL) was slowly
added dropwise to a solution of ligand 9 (70 mg, 0.255 mmol)
Table 3. Basic crystallographic data and structure refinement parameters for compounds 6b—d, 8, and 10
Parameter
6b
6c
6d
8
10
Molecular formula
C15H15ClN2OPdS C17H13ClN2OPdS C26H21ClNOPPdS2 C33H37Cl9NOPPdS2 C14H13ClN2O2PdS
Molecular weight
T/K
413.20
120
435.20
120
600.38
100
984.18
120
415.17
120
Crystal system
Space group
Z
Orthorhombic
Pna21
4
Orthorhombic
Pbcn
Monoclinic
P21/c
Monoclinic
P21/n
Triclinic
Pꢀ1
8
4
4
4
a/Å
b/Å
c/Å
α/deg
β/deg
γ/deg
9.0597(8)
19.0784(17)
8.7568(8)
—
18.8499(12)
10.3731(7)
16.1984(10)
—
9.107(3)
21.107(8)
13.158(5)
—
103.545(9)
—
2458.8(15)
1.622
11.19
16.0079(4)
15.8962(4)
16.4646(4)
—
102.2730(10)
—
10.2663(5)
11.5916(6)
12.6465(7)
104.1130(10)
90.6280(10)
91.5550(10)
1458.77(13)
1.890
—
—
—
—
3
V/Å
1513.6(2)
1.813
15.39
3167.3(4)
1.825
14.76
4093.91(18)
1.597
dcalc/g cm–3
μ/cm–1
12.11
16.02
F(000)
824
1728
1208
1984
824
2θmax/deg
58
58
58
52
58
Reflection collected
Number of independent
reflections
14654
3989
17931
4210
19869
6544
30516
7979
17662
7748
Number of reflections
with I > 2σ(I)
Number of refined
parameters
3750
190
3405
208
5601
298
7492
451
6834
379
R1
wR2
0.0269
0.0618
0.0467
0.1486
0.0257
0.0595
0.0659
0.2435
0.0248
0.0588
GOF
1.007
1.084
1.001
2.027
1.007
Residual electron
density/e Å–3, ρmax/ρ
1.136/–0.817
0.890/–1.122
0.510/–0.592
1.361/–1.752
0.707/–0.850
min

Amides of mercaptoacetic and propionic acids
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 11, November, 2015 2689
DMF was added via a syringe.10b,18 The tube was filled with
argon, the reaction mixture was stirred for 5 h at 120 °C. An
aliquot of the reaction mixture was diluted with water, extracted
with benzene, and analyzed by GC (a 25ꢀm capillary column,
SEꢀ30, 150—250 °C at the rate of heating 15 °C min–1). The
chromatographic patterns contained peaks of the starting comꢀ
pounds 11a,b and the crossꢀcoupling products 12a,b (the retenꢀ
tion times were the same as those of the authentic samples).
Sometimes we observed the formation of an insignificant amount
of biphenyl (the product of homocoupling of phenylboronic acid
taken in the excess), which was not taked into account in the
calculation of the chromatographic patterns. We assumed that
chemically stable compounds 11a,b and 12a,b in the course of
the process do not undergo resinification, and the yields of the
products 12 were considered to be equal to the conversions of
the starting compounds 11.
Xꢀray diffraction study. Single crystals of compounds 6b—d,
8, and 10 were obtained by crystallization from CH2Cl2—hexꢀ
ane (6b), CHCl3—Et2O (6c, 10), CHCl3—hexane (6d), and
CH2Cl2—CCl4 (8). Xꢀray diffraction studies of complexes 6b, 10
and 6c, 6d, 8 were carried out on Bruker APEX2 CCD and
Bruker APEX2 DUO CCD diffractometers, respectively (MoꢀKα
radiation, graphite monochromator, ωꢀscan mode). The strucꢀ
tures were solved by direct method and refined by the fullꢀmatrix
least squares method against F2hkl in anisotropic approximation.
Positions of hydrogen atoms were calculated geometrically in
isotropic approximation, using a riding model. The main crysꢀ
tallographic data and parameters of refinement are given in
Table 3. All the calculations were carried out using the SHELXTL
PLUS program package.19
(f) S. Mahadik, S. A. Knott, L. F. Szczepura, S. R. Hitchꢀ
cock, Tetrahedron: Asymmetry, 2009, 20, 1132.
6. (a) J. D. G. Correia, A. Domingos, I. Santos, H. Spies,
J. Chem. Soc., Dalton Trans., 2001, 2245; (b) E. Palma,
J. D. G. Correia, A. Domingos, I. Santos, R. Alberto,
H. Spies, J. Organomet. Chem., 2004, 689, 4811.
7. (a) H. Sakurai, H. Uchikubo, K. Ishizu, K. Tajima, Y. Aoyaꢀ
ma, H. Ogoshi, Inorg. Chem., 1988, 27, 2691; (b) M. M.
Morlok, K. E. Janak, G. Zhu, D. A. Quarless, G. Parkin,
J. Am. Chem. Soc., 2005, 127, 14039; (c) J. G. Melnick,
K. Yurkerwich, G, Parkin, J. Am. Chem. Soc., 2010, 132, 647.
8. (a) Y. Singh, R. Sharan, R. N. Kapoor, Ind. J. Chem., Sect.
A: Inorg., Phys., Theor. Anal., 1986, 25A, 771; (b) Y. Singh,
R. Sharan, R. N. Kapoor, Synth. React. Inorg. Met.ꢀOrg.
Chem., 1986, 16, 1225; (c) S. C. Dixit, R. Sharan, R. N.
Kapoor, J. Organomet. Chem., 1987, 332, 135; (d) A. K. Narula,
P. Lukose, J. Organomet. Chem., 1990, 393, 365.
9. (a) P. J. Toscano, L. G. Marzilli, Inorg. Chem., 1983, 22,
3342; (b) P. J. Toscano, K. J. Fordon, D. Macherone,
S. Liu, J. Zubieta, Polyhedron, 1990, 9, 2375; (c) E. L. Klein,
M. A. Khan, R. P. Houser, Inorg. Chem., 2004, 43, 7272;
(d) M. J. AlꢀJeboori, H. H. AlꢀTawel, R. M. Ahmad, Inorg.
Chim. Acta, 2010, 363, 1301.
10. A. A. Vasil´ev, V. Yu. Aleksenko, D. V. Aleksanyan, V. A.
Kozlov, Mendeleev Commun., 2013, 23, 344.
11. J. A. Davies, F. R. Hartley, Chem. Rev., 1981, 81, 79.
12. L. J. Bellamy, The Infrared Spectra of Complex Molecules,
Wiley, New York, 1975.
13. Y. Zhang, Z. Li, X. Cao, J. Zhao, J. Mol. Catal. A: Chem.,
2013, 366, 149.
14. A. Shockravi, M. Chaloosi, E. Rostami, D. Heidaryan,
A. Shirzadmehr, H. Fattahi, H. Khoshsafar, Phosphorus, Sulꢀ
fur Silicon Relat. Elem., 2007, 182, 2115.
References
15. V. Yu. Aleksenko, E. V. Sharova, O. I. Artyushin, D. V.
Aleksanyan, Z. S. Klemenkova, Yu. V. Nelyubina, P. V.
Petrovskii, V. A. Kozlov, I. L. Odinets, Polyhedron, 2013,
51, 168.
16. US Pat. 2005/0169863; http://worldwide.espacenet.com/
publicationDetails/originalDocument?CC=US&NR=
2005169863A1&KC=A1&FT=D&ND=3&date=20050804
&DB=worldwide.espacenet.com&locale=en_EP.
17. E. S. Izmest´ev, D. V. Sudarikov, S. A. Rubtsova, P. A.
Slepukhin, A. V. Kuchin, Russ. J. Org. Chem. (Engl. Transl.),
2012, 48, 184 [Zh. Org. Khim., 2012, 48, 197].
18 (a) D. V. Aleksanyan, V. Yu. Aleksenko, Yu. V. Nelyubina,
A. A. Vasil´ev, R. R. Aysin, Z. S. Klemenkova, V. A. Kozlov,
P. V. Petrovskii, I. L. Odinets, Inorg. Chim. Acta, 2013, 404,
167; (b) D. V. Aleksanyan, O. I. Artyushin, G. K. Genkina,
A. A. Vasil´ev, Yu. V. Nelyubina, N. E. Shepel´, Z. S. Kleꢀ
menkova, L. V. Gumileva, V. A. Kozlov, Russ. Chem. Bull.
(Int. Ed.), 2014, 63, 2309 [Izv. Akad. Nauk, Ser. Khim., 2014,
2309]; (c) I. M. Aladzheva, O. V. Bykhovskaya, A. A.
Vasil´ev, Yu. V. Nelyubina, Z. S. Klemenkova, Russ. Chem.
Bull. (Int. Ed.), 2015, 64, 909 [Izv. Akad. Nauk, Ser. Khim.,
2015, 909].
1. (a) O. Belda, C. Moberg, Coord. Chem. Rev., 2005, 249, 727;
(b) A. Rajput, R. Mukherjee, Coord. Chem. Rev., 2013,
257, 350.
2. (a) A. K. Singh, R. Mukherjee, J. Chem. Soc., Dalton Trans.,
2005, 2886; (b) S. Nag, R. J. Butcher, S. Bhattacharya, Eur.
J. Inorg. Chem., 2007, 1251; (c) A. K. Singh, R. Mukherjee,
Dalton Trans., 2008, 260; (d) A. K. Sharma, S. Biswas, S. K.
Barman, R. Mukherjee, Inorg. Chim. Acta, 2010, 363, 2720;
(e) D. V. Aleksanyan, Yu. V. Nelyubina, Z. S. Klemenkova,
V. A. Kozlov, Phosphorus, Sulfur Silicon Relat. Elem., 2014,
189, 1028.
3. A. Decken, R. A. Gossage, P. N. Yadav, Can. J. Chem.,
2005, 83, 1185.
4. (a) S. J. Brown, X. Tao, D. W. Stephan, P. K. Mascharak,
Inorg. Chem., 1986, 25, 3377; (b) L. A. Tyler, J. C. Noveron,
M. M. Olmstead, P. K. Mascharak, Inorg. Chem., 2000,
39, 357.
5. (a) S. Ongeri, U. Piarulli, M. Roux, C. Monti, C. Gennari,
Helv. Chim. Acta, 2002, 82, 3388; (b) Ch. M. Tomas, R. Maꢀ
fua, Br. Therrien, E. Rusanov, H. StoeckliꢀEvans, G. Süssꢀ
Fink, Chem. Eur. J., 2002, 8, 3343; (c) H. Y. Kwon, S. Y.
Lee, B. Y. Lee, D. M. Shin, Y. K. Chung, Dalton Trans.,
2004, 921; (d) S. Burger, B. Therrien, G. SüssꢀFink, Helv.
Chim. Acta, 2005, 88, 478; (e) V. R. Marinho, A. I. Rodꢀ
rigues, A. J. Burke, Tetrahedron: Asymmetry, 2008, 19, 454;
19. G. M. Sheldrick, Acta Crystallogr. A, 2008, 64, 112.
Received April 27, 2015