Crystal structures of β-chalcogeno-α, β-unsaturated chalcogenoesters: Novel intramolecular interaction between the carbonyl oxygen and the chalcogen atom at the β-position

Article abstract of DOI:10.1002/hc.20690

A series of β-chalcogeno-α, β-unsaturated chalcogenoesters (1 and 2) were synthesized, and their molecular structures were investigated in detail by X-ray crystal analyses. Interestingly, intramolecular interactions between the carbonyl oxygen and the chalcogen atom at the β-position (β-S ...O and β-Se...O) were observed in most cases, and intermolecular π-π interaction and hydrogen bonding were observed in the case of δ-hydroxy derivatives (1b and 2b).

Full text of DOI:10.1002/hc.20690

Heteroatom Chemistry
Volume 22, Number 3/4, 2011
Crystal Structures of β-Chalcogeno-α,β-
unsaturated Chalcogenoesters: Novel
Intramolecular Interaction between the
Carbonyl Oxygen and the Chalcogen Atom
at the β-Position
Toshiya Ozaki, Akihiro Nomoto, and Akiya Ogawa
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
1-1 Gakuen-cho, Naka-ku, Sakai, Osaka 599–8531, Japan
Received 12 September 2010; revised 29 October 2010
ized molecules [1]. Although the numerous multi-
ABSTRACT:
A
series of β-chalcogeno-α, β-
functionalized compounds have been synthesized by
multistep procedures, we have developed a series
of unique methodology for simultaneous introduc-
tion of heteroatom moieties to unsaturated bonds on
the basis of the transition-metal-catalyzed reactions
[2]. For example, organic disulfides and diselenides
add to terminal alkynes stereoselectively to give the
corresponding (Z)-vic-dichalcogenoalkenes (Eq. (1))
[3a].
unsaturated chalcogenoesters (1 and 2) were
synthesized, and their molecular structures were
investigated in detail by X-ray crystal analyses.
Interestingly, intramolecular interactions between
the carbonyl oxygen and the chalcogen atom at the
β-position (β-S· · ·O and β-Se· · ·O) were observed
in most cases, and intermolecular π–π interac-
tion and hydrogen bonding were observed in the
ꢀ
C
case of δ-hydroxy derivatives (1b and 2b).
2011
Wiley Periodicals, Inc. Heteroatom Chem 22:579–585,
2011; View this article online at wileyonlinelibrary.com.
DOI 10.1002/hc.20690
cat. Pd(PPh3)4
(Y=S, Se)
R
+ (R'Y)2
R
YR'
R'Y
(1)
Furthermore, when the same catalytic reac-
INTRODUCTION
tions of dichalcogenides with alkynes are conducted
under the pressurized carbon monoxide, highly
selective carbonylative addition to alkynes takes
place, affording the corresponding β-chalcogeno-
α,β-unsaturated chalcogenoesters (1 or 2) with ex-
cellent regio- and stereoselectivities (Eq. (2)) [3].
Catalytic addition of heteroatom compounds to un-
saturated bonds in the presence of transition metal
complexes is becoming an increasingly powerful
method for the construction of various functional-
Dedicated to Professor Kin-ya Akiba on the occasion of his 75th
birthday.
Correspondence to: Akiya Ogawa; e-mail: ogawa@chem.osakafu-
u.ac.jp; A. Nomoto; e-mail: nomoto@chem.osakafu-u.ac.jp.
Contract grant sponsor: Ministry of Education, Culture, Sports,
Science and Technology, Japan.
R
YR'
cat. Pd(PPh3)4
+ (R'Y)2
+
CO
R
R'Y
1 (Y=S)
2 (Y=Se)
O
Contract grant number: B, 19350095
2011 Wiley Periodicals, Inc.
c
ꢀ
(2)
579

580 Ozaki, Nomoto, and Ogawa
By using these highly selective methods, we have
prepared a wide range of heteroatom-containing
vinylic compounds so far. During these investiga-
tions, we are interested in the molecular structures
of vicinally bifunctionalized alkenes, especially cis-
isomers of β-chalcogeno-α,β-unsaturated chalcoge-
noesters (1 and 2), because interaction between
heteroatoms can be investigated in detail [4]. In
this paper, we report the structural properties by
X-ray crystal analyses and IR spectral analyses of
β-chalcogeno-α, β-unsaturated chalcogenoesters (1
and 2).
between the O-atom of the carbonyl group and the
S-atom of S C C moiety are 2.796, 2.830, 2.842,
and 3.070 A, respectively, and these are shorter than
˚
the sum of van der Waals radii of sulfur and oxy-
˚
gen (3.32 A) (Table 1) [7]. As a result, a widespread
planar arrangement was observed as torsion an-
gles between S C C and C( O) S in 1a–1d are
177.31◦, 179.61◦, 175.37◦, and 178.80◦, respectively.
In thioesters 1a–1c, the angles for nonbonded O· · ·
S Cipso are 167.49◦, 173.75◦, and 165.52◦, and there-
fore Cipso, S, and O are located approximately in line.
In contrast, the angles for nonbonded O· · · S-Cipso of
1d is 69.11◦; in addition, the S· · ·O distance of 1d
is longer than those of 1a–1c. These results strongly
suggest that, in the cases of 1a–1c, the σ*–n interac-
tion between the S-atom of S C C moiety and the
carbonyl oxygen contributes to the lower carbonyl
wavenumber in IR spectra and the shorter S· · ·O
distance [8]. In the case of 1d, however, the non-
linear relationship of Cipso, S, and O and the longer
S· · ·O distance indicate lack of such the σ*–n inter-
action, resulting in the normal IR value of carbonyl
wavenumber. The nonlinear relationship of Cipso, S,
and O may be due to the bulkiness of 1-hydroxy-
cyclohexyl group and the CH–π interaction between
the phenyl group and cyclohexyl group.
RESULTS AND DISCUSSION
Among the β-chalcogeno-α, β-unsaturated chalcoge-
noesters synthesized, we succeeded in X-ray analy-
ses of the following seven compounds (1a–1d and
2a–2c). Scheme 1 shows the chemical structures
of the seven compounds and also their carbonyl
wavenumbers of IR spectra in solid and in solution,
comparing with that of chalcogenoester 3 [5,6].
As can be seen from Scheme 1, the car-
bonyl wavenumbers in solid of β-chalcogeno-α,β-
unsaturated chalcogenoesters (1 and 2) except 1d
are lower compared with that of 3 (see, the values ob-
tained by using the KBr method). Next, we focused
on the structures of sulfur-containing compounds
(1a–1d) and each molecular structure by X-ray anal-
ysis is shown in Fig. 1. The nonbonded distances
Figure 2 indicates the results of the X-ray anal-
yses of the corresponding selenoesters 2. The sele-
noesters (2a–2c) show almost the same structures
as those of the thioesters 1a–1c. The torsion angles
SPh
HO
SPh
SPh
SPh
HO
PhS
PhS
O
PhS
O
PhS
O
O
1a
1b
1c
1d
ν
C=O 1661 cm 1 (KBr)
1670 cm 1(20 mM)
ν
C=O 1641 cm 1 (KBr)
1670 cm 1(20 mM)
ν
C=O 1662 cm 1 (KBr)
1668 cm 1(20 mM)
ν
C=O 1684 cm 1 (KBr)
1697 cm 1(20 mM)
SePh
HO
SePh
PhSe
SePh
Ph
O
SePh
PhSe
O
PhSe
O
2
O
2a
2b
3
2c
ν
C=O 1658 cm 1 (KBr)
1668 cm 1(20 mM)
ν
C=O 1637 cm 1 (KBr)
1670 cm 1(20 mM)
ν
C=O 1654 cm 1 (KBr)
ν
C=O 1685cm 1 (KBr)
1684 cm 1(20 mM)
1
1670 cm (20 mM)
SCHEME 1 IR spectra of carbonyl group of chalcogenoesters (1–3) in solid and in solution.
Heteroatom Chemistry DOI 10.1002/hc

Crystal Structures of β-Chalcogeno-α,β-Unsaturated Chalcogenoesters 581
TABLE 2 Selected Distances and Angles for 2a–2c
TABLE 1 Selected Distances and Angles for 1a–1d
Product
1a
1b
1c
1d
Product
2a
2b
2c
˚
˚
S· · · ·O distance (A)
2.796
2.830
2.842
3.070
Se· · ·O distance (A)
Torsion angle between
Se C C and C( O) Se (◦)
Angle for nonbonded
O· · ·Se Cipso (◦)
2.791
2.801
2.735
Torsion angle between 177.31 179.61 175.37 178.80
176.64 178.80 167.31
S C C and
C( O) S (◦)
168.20 174.97 171.43
Angle for nonbonded
167.49 173.75 165.52
˚
69.11
O· · ·S Cipso (◦)
˚
The sum of van der Waals radii (Se· · ·O): 3.42 A.
The sum of van der Waals radii (S· · ·O): 3.32 A.
groups take part to form intermolecular π–π stack-
ing (3.53 A; 1b, 3.55 A; 2b), and hydroxy groups
between Se C C and C( O) Se indicate the pla-
narity of Se C C C( O) Se unit (Table 2). The
angles for nonbonded O· · ·Se Cipso indicate that
Cipso, Se, and O are located approximately on line.
These results and the lower carbonyl wavenumbers
strongly suggest the σ*–n interaction between the
Se-atom of Se C C moiety and the carbonyl oxygen.
Considering that the van der Waals radius of
Se· · ·O (3.42 A) is longer than that of S· · ·O (3.32 A),
the σ*–n interaction selenoesters 2 is somewhat
stronger, compared with thioesters 1a–1c [9].
Next, we examined to clarify the packing struc-
tures of thioesters 1 and selenoesters 2. In the pack-
ing structures of 1a, 1c, 1d, 2a, and 2c, significant
intermolecular interactions were not observed. In
the cases of 1b and 2b, however, remarkable π–π
stacking interactions and hydrogen bondings were
observed (Fig. 3). The phenyl rings of SPh or SePh
˚
˚
are available for participating in intermolecular hy-
˚
drogen bonding with carbonyl groups (2.77 A; 1b,
˚
2.87 A; 2b). Interestingly, the packing structures of
1b and 2b are almost the same despite of different
atoms, i.e., S and Se.
Scheme 1 also indicates the IR values in solu-
tion of the carbonyl group of chalcogenoesters 1–3.
By comparing the values in solution with those in
solid, an increase in ca. 10 cm−1 was observed in the
cases of 1a, 1c, 2a, and 2c. On the other hand, the
increase in ca. 30 cm−1 was observed in the cases
of 1b and 2b, which suggests the strong hydrogen
bonding is present in solid state. In all cases that
the σ*–n interaction is observed (1a–1c and 2a–2c),
the wavenumbers of carbonyl groups in solution are
lower than that of β-chalcogeno-unsubstituted 3.
˚
˚
FIGURE 1 Molecular structures of 1a–1d.
Heteroatom Chemistry DOI 10.1002/hc

582 Ozaki, Nomoto, and Ogawa
FIGURE 2 Molecular structures of 2a–2c.
CONCLUSIONS
as the solvent. The purification of the products was
carried out by medium-pressure liquid chromatog-
raphy (MPLC; silica gel, 25–40 μm, length 310 mm,
i.d. 25 mm) and preparative TLC (PTLC) on B-5F
silica gel (Wako Ltd., Osaka, Japan).
Details of the X-ray analyses and IR spectral analyses
of β-chalcogeno-α,β-unsaturated chalcogenoesters
(1 and 2) have been revealed. Interestingly, the σ*–
n interaction between the chalcogen atom bonded
directly to vinyl and the carbonyl oxygen has been
According to the reported procedure [3a], to a
two-necked 5 mL reaction vessel equipped with a
magnetic stirring bar, Pd(PPh3)4 (24 mg, 0.02 mmol),
toluene (2.0 mL), alkynes (1.0 mmol), and diphenyl
disulfide or diphenyl diselenide (1.0 mmol) were
added. The mixture was heated at 80◦C for 19 h un-
der the pressure of carbon monoxide (1–60 atm).
The reaction mixture was filtered through Celite and
purified by MPLC and PTLC to give the objective
substances. Recrystallization for X-ray analyses was
carried out from solutions of 1a (ethyl acetate), 1b
(diethyl ether), 1c (ethyl acetate), 1d (n-hexane), 2a
(ethyl acetate), 2b (benzene), and 2c (benzene).
observed, based on the linear relationship of Cipso
,
S (Se), and O and the shorter S (Se)· · ·O distance
[10]. The σ*–n interaction effects the decrease in IR
values of carbonyl groups. In pharmaceutical [11]
or materials science [12], molecular structure and
packing structure in crystal play important roles to
realize each functionality, and therefore, we believe
that this study will make great contributions and
store-rich knowledge in the scientific fields.
EXPERIMENTAL
General
IR Measurements
1H NMR spectra were recorded on JNM-GSX 270
(270 MHz; JEOL Ltd., Tokyo, Japan) spectrometers
using CDCl3 as the solvent with Me4Si as the internal
standard. 13C NMR spectra were taken on JNM-GSX
270 (68 MHz; JEOL Ltd.) spectrometers using CDCl3
Infrared spectra were determined on a Perkin Elmer
Model 1600 spectrometer (PerkinElmer Japan Co.,
Ltd., Yokohama, Japan) or FT/IR-8900 μ Fourier
Transform Infrared Microsampling System (JASCO
Heteroatom Chemistry DOI 10.1002/hc

Crystal Structures of β-Chalcogeno-α,β-Unsaturated Chalcogenoesters 583
(a)
HO
OH
S
S
O
S
Hydrogen bond
HO
S
O
S
S
O
S
O
S
OH
Hydrogen bond
O
S
OH
S
S
S
O
OH
OH
(b)
HO
Se
Se
O
Se
Hydrogen bond
HO
Se
O
Se
O
Se
Se
O
Se
OH
Hydrogen bond
O
Se
OH
Se
Se
Se
O
OH
FIGURE 3 Packing structures of 1b (a) and 2b (b).
(m, 3 H), 7.52–7.53 (m, 2 H); 13C NMR (68 MHz,
CDCl3) δ 121.02, 127.83, 128.01, 128.11, 128.43,
128.66, 128.93, 129.14, 129.32, 132.06, 134.17,
134.67, 137.74, 158.63, 185.19; IR (KBr) 3059, 1661,
1537, 1078, 949, 791, 752, 705, 690, 671, 588 cm−1;
mass spectrum (CI), m/z 349 (M+ +1, 100). Anal.
Calcd for C21H16OS2: C, 72.38; H, 4.62; S, 18.40.
Found C, 72.37; H, 4.61; S, 18.32.
Inc., Tokyo, Japan). The carbonyl wavenumbers
were measured in the transmittance scale mode for
20 mM solution or KBr pellet.
X-Ray Structure Determination
X-ray crystallographic measurements were carried
out on a RAXIS-RAPID diffractometer (RIGAKU
Corp., Tokyo, Japan) with Mo Kα radiation. The
structure was solved by direct methods. All hydro-
gen atoms were located in different Fourier maps,
but for consistency they were included in the final
refinement in idealized positions. Final refinement
was carried out by full-matrix least squares proce-
dures.
(Z)-1,3-Bis(phenylthio)-5-hydroxy-2-penten-1-
one (1b)
1
mp 110–112◦C (a white solid); H NMR (270 MHz,
CDCl3) δ 1.46 (t, J = 5.4 Hz, 1 H), 2.41 (t, J = 6.4 Hz,
2 H), 3.58, (q, J (average) = 5.9 Hz, 2 H), 6.35 (s, 1
H), 7.34–7.55 (m, 10 H); 13C NMR (68 MHz, CDCl3) δ
39.20, 60.95, 118.64, 127.93, 129.05, 129.23, 129.27,
129.69, 130.07, 134.60, 135.62, 157.15, 185.16; IR
(KBr) 3531, 2872, 1641, 1537, 1476, 1439, 1111,
1073, 1046, 842, 748, 706 cm−1; mass spectrum (CI),
(Z)-1,3-Bis(phenylthio)-3-phenyl-2-propen-1-one
(1a)
1
mp 135–139◦C (a yellow solid); H NMR (270 MHz,
CDCl3) δ 6.45 (s, 1 H), 7.03–7.13 (m, 10 H), 7.43–7.44
Heteroatom Chemistry DOI 10.1002/hc

584 Ozaki, Nomoto, and Ogawa
m/z 317 (M+ + 1, 100). Anal. Calcd for C17H16O2S2:
C, 64.53; H, 5.10; S, 20.26. Found C, 64.46; H, 5.09;
S, 20.12.
2c
P
(Z)-1,3-Bis(phenylthio)-3-(1-cyclohexenyl)-2-
propene-1-one (1c)
mp 95.5–96.5◦C (light yellow crystal); 1H NMR
(270 MHz, CDCl3) δ 1.08–1.14 (m, 2H), 1.26–1.29 (m,
2H), 1.78 (m, 2H), 1.87–1.90 (m, 2H), 5.76 (m, 1H),
6.29 (s, 1H), 7.24–7.30 (m, 3H), 7.35–7.43 (m, 4H),
7.44–7.50 (m, 3H); 13C NMR (68 MHz, CDCl3) δ 21.33,
21.88, 25.11, 28.89, 118.05, 128.31, 129.02, 129.15,
130.93, 132.51, 134.59, 134.63, 136.28, 161.92,
185.44; IR (KBr) 2934, 1662, 1542, 1474, 1438, 1184,
1039, 904, 748, 690, 616, 606, 528 cm−1; mass spec-
trum (CI), m/z 353 (M+ + 1, 50). Anal. Calcd for
C21H20OS2: C, 71.55; H, 5.72; S, 18.19. Found C,
71.59; H, 5.63; S, 18.09.
2b
cP
2a
(Z)-1,3-Bis(phenylthio)-3-(1-hydroxy-cyclohexyl)-
2-propene-1-one (1d)
1
mp 86◦C–87◦C (yellow crystal) H NMR (270 MHz,
cP
CDCl3) δ 1.23 (m, 1H), 1.53–1.77 (m, 7H), 1.88–1.97
(m, 2H), 2.21 (s, 1H), 6.92 (s, 1H), 7.04–7.08 (m, 2H),
7.15–7.33 (m, 8H); 13C NMR (68 MHz, CDCl3) δ 21.58,
25.11, 35.76, 76.11, 125.97, 126.58, 127.71, 128.92,
128.96, 129.13, 129.79, 134.33, 135.36, 158.01,
186.51; IR (KBr) 3427, 3057, 2924, 1684, 1567, 1478,
1439, 1098, 1039, 1020, 883, 844, 735, 686, 581 cm−1;
mass spectrum (CI) m/z 371 (M+ + 1, 8). Anal. Calcd
for C21H22O2S2: C, 68.07; H, 5.98; S, 17.31. Found C,
67.98; H, 5.97; S, 17.24.
1d
cP
1c
P
(Z)- 1,3-Bis(phenylseleno)-3-phenyl-2-propen-l-
one (2a)
mp 135◦C–141◦C (yellow crystal); 1H NMR
(270 MHz, CDCl3) δ 6.80 (s, 1 H), 6.95–7.08
(m, 8 H), 7.19 (d, 2 H, J = 6.8 Hz), 7.40–7.42
(m, 3 H), 7.60–7.62 (m, 2 H); 13C NMR (68 MHz,
CDCl3) δ 124.73, 126.66, 127.57, 128.09, 128.33,
128.45, 128.67, 128.93, 129.05, 129.37, 135.79,
136.05, 138.58, 159.57, 187.77; IR (KBr) 3057, 1658,
1531, 1486, 1476, 1437, 1227, 1042, 935, 760, 744,
696 cm−1; mass spectrum (CI), m/z 439 (M+ + 1,
56). Anal. Calcd for C21H16OSe2: C, 57.03; H, 3.64.
Found C, 57.19; H, 3.64.
1b
cP
1a
P
(Z)-1,3-Bis(phenylseleno)-5-hydroxy-2-penten-1-
one (2b)
mp 83–84◦C (yellow solid); 1H NMR (270 MHz,
R
a
b
c
V
D
R
W
CDCl3) δ 1.63 (br, 1 H), 2.41 (t, J = 6.7 Hz, 2 H),
Heteroatom Chemistry DOI 10.1002/hc

Crystal Structures of β-Chalcogeno-α,β-Unsaturated Chalcogenoesters 585
J Am Chem Soc 1995, 117, 7564; (d) Kawakami, J.;
3.52, (t, J = 6.3 Hz, 2 H), 6.75 (s, 1 H), 7.33–7.48
(m, 10 H); 13C NMR (68 MHz, CDCl3) δ 29.92,
61.33, 115.17, 129.08, 129.50, 129.54, 129.72, 130.25,
135.93, 136.78, 137.35, 137.59, 157.82, 187.97; IR
(KBr) 3554, 1637, 1521, 1473, 1438, 1103, 1068,
1037, 1020, 999, 823, 800, 740, 686 cm−1; HRMS
(FAB): Calcd for C17H17O2Se2, 412.9559: Found
412.9563.
Takeba, M.; Kamiya, I.; Sonoda, N.; Ogawa, A. Tetra-
hedron 2003, 59, 6559; (e) Ogawa, A.; Kawakami,
J.; Mihara, M.; Ikeda, T.; Sonoda, N.; Hirao, T. J
Am Chem Soc 1997, 119, 12380; (f) Kawakami, J.;
Mihara, M.; Kamiya, I.; Takeba, M.; Ogawa, A.;
Sonoda, N. Tetrahedron 2003, 59, 3521.
[4] (a) Akiba, K.-y.; Takee, K.; Ohkata, K.; Iwasaki, K.
J Am Chem Soc 1983, 105, 6965; (b) Akiba, K.-y.;
Takee, K.; Shimizu, Y.; Ohkata, K. J Am Chem Soc
1986, 108, 6320; (c) Akiba, K.-y. In Chemistry of
Hypervalent Compounds; Akiba, K.-y. (Ed.); Wiley-
VCH: Weinheim, Germany, 1999; Ch. 1 and 2; (d)
Kawashima, T. In Chemistry of Hypervalent Com-
pounds; Akiba, K.-y. (Ed.); Wiley-VCH: Weinheim,
Germany, 1999; Ch. 6; (e) Akiba, K.-y.; Yamamoto,
Y. Heteroatom Chem 2007, 18, 161.
[5] (a) Guerrero, S. A.; Barros, J. R. T.; Wladislaw, B.;
Rittner, R.; Olivato, P. R. J Chem Soc, Perkin Trans
II 1983, 1053; (b) Olivato, P. R.; Guerrero, S. A.; Hase,
Y.; Rittner, R. J Chem Soc, Perkin Trans II 1990, 465;
(c) Olivato, P. R.; Guerrero, S. A.; Lopes, J. C. D.;
Hase, Y.; Still, I. W.; Wilson, D. K. T. Phosphorous,
Sulfur Silicon Relat Elem 1993, 82, 7.
(2Z, 8Z)-1,3,8,10-Tetrakis(phenylseleno)-2,8-
decadien-1,10-dione (2c)
1
mp 114–115◦C (yellow solid); H NMR (270 MHz,
CDCl3) δ 1.02 (br s, 4H), 1.91 (br s, 4H), 6.52 (s,
2H), 7.30–7.43 (m, 12H), 7.54–7.60 (m, 8H); 13C
NMR (68 MHz, CDCl3) δ 28.74, 37.00, 122.33, 126.59,
127.12, 129.23, 129.31, 129.43, 135.76, 137.19,
161.75, 187.46; IR (KBr) 3056, 2953, 1654, 1541,
1477, 1438, 1093, 1070, 1020, 819, 793, 738, 685,
540, 489 cm−1; mass spectrum (CI), m/z 791 (M++1,
6); Anal. Calcd for C34H30O2Se4: C, 51.93; H, 3.84.
Found C, 52.05; H, 3.82.
[6] Beletskaya, I. P.; Sigeev, A. S.; Peregudov, A. S.; Petro-
vskii, P. V. Russ J Org Chem 2001, 37, 1703.
[7] (a) Lynch, T. R.; Mellor, I. P.; Nyburg, S. C. Acta Cryst
B 1971, 27, 1948; (b) Mellor, I. P.; Nyburg, S. C. Acta
Cryst B 1971, 27, 1954; (c) Beer, R. J. S.; McMonagle,
D.; Siddiqui, M. S. S. Tetrahedron 1979, 35, 1199; (d)
ACKNOWLEDGMENT
´
´
Angya´n, J. G.; Poirier, R. A.; Kucsman, A.; Csizmadia,
I. G. J Am Chem Soc 1987, 109, 2237; (e) Cohen-
Addad, C.; Lehmann, M. S.; Becker, P.; Pa´rka´nyi, L.;
Ka´lman, A. J Chem Soc, Perkin Trans II 1984, 191; (f)
Fabius, B.; Cohen-Addad, C.; Larsen, F. K.; Lehmann,
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We thank all participants of “The 45th Seminar of
Heteroatom Chemistry in Tsukuba, Japan” for their
informative suggestions.
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Heteroatom Chemistry DOI 10.1002/hc