Reaction of quinoline-5,8-diones with selected charged phosphorus nucleophiles

Article abstract of DOI:10.1080/10426507.2011.626472

The redox reactivity of the two quinoline-5,8-dione derivatives2-methyl-5, 8-dioxo-5,8-dihydroquinoline-7-amine (2a) and N-(2-methyl-5,8-dioxo-5,8- dihydroquinolin-7-yl)acet-amide (2b)has been demonstrated by their reaction with negatively charged three-c

Full text of DOI:10.1080/10426507.2011.626472

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Phosphorus, Sulfur, and Silicon and the
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Reaction of Quinoline-5,8-Diones
with Selected Charged Phosphorus
Nucleophiles
a
a
b
Jacek E. Nycz , Grzegorz Malecki , Samir Chikkali , Imre Hajdok
b
b
&
Priti Singh
a
Institute of Chemistry , University of Silesia , ul. Szkolna 9,
PL-40007 , Katowice , Poland
b
Institute of Inorganic Chemistry , University of Stuttgart ,
Pfaffenwaldring 55, 70550 , Stuttgart , Germany
Published online: 27 Mar 2012.
To cite this article: Jacek E. Nycz , Grzegorz Malecki , Samir Chikkali , Imre Hajdok & Priti Singh
(2012) Reaction of Quinoline-5,8-Diones with Selected Charged Phosphorus Nucleophiles, Phosphorus,
Sulfur, and Silicon and the Related Elements, 187:5, 564-572, DOI: 10.1080/10426507.2011.626472
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Phosphorus, Sulfur, and Silicon, 187:564–572, 2012
Copyright ꢀ
Taylor & Francis Group, LLC
C
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.626472
REACTION OF QUINOLINE-5,8-DIONES WITH SELECTED
CHARGED PHOSPHORUS NUCLEOPHILES
1
1
2
Jacek E. Nycz, Grzegorz Malecki, Samir Chikkali,
2
2
Imre Hajdok, and Priti Singh
Institute of Chemistry, University of Silesia, ul. Szkolna 9, PL-40007 Katowice,
Poland
1
2
Institute of Inorganic Chemistry, University of Stuttgart, Pfaffenwaldring 55,
70550 Stuttgart, Germany
GRAPHICAL ABSTRACT
O
O
R
R
SET
THF
P
YM
+
+
P
Y
R'
R'
R"HN
N
Me
R"HN
N
Me
O
O-
M+
R" = H, COMe; M = Li, Na; Y = O, lone pair;
R = Ph, tBu; R' = Ph; R = R' = OEt; R/R' = OCH CMe CH O
2
2
2
Abstract The redox reactivity of the two quinoline-5,8-dione derivatives—2-methyl-5,8-dioxo-
,8-dihydroquinoline-7-amine (2a) and N-(2-methyl-5,8-dioxo-5,8-dihydroquinolin-7-yl)acet-
5
amide (2b)—hasbeen demonstrated by their reaction with negatively charged three-coordinated
phosphorus nucleophiles, such as R2P-YM (1a–d, Y = O or lone pair; R = Ph, tBu,
OCH2CMe2CH2O, or EtO; M = Li or Na). 1a–d participated in single-electron transfer
(SET) to 2a and 2b, generating the radical anions 3 and 4, respectively, together with short-
lived phosphorus-centered radical intermediates of type R2P( = Y)· (5). The radicals 5 dimerize
to give R2P(Y)–(Y)PR2 (6). Both 3 and 4 are remarkably persistent with half-lives of more than
1
month in THF (tetrahydrofuran) at 300 K.
Keywords Quinone; lavendamycin; EPR spectroscopy; streptonigrin; quinoline; radical
INTRODUCTION
Streptonigrin (also known as rufochromomycin and bruneomycin), lavendamycin
Scheme 1), and other similar compounds are well-known aminoquinones with a quinoline-
(
5,8-dione subunit, which contributes to their reactivity and biological activity. Streptonigrin
and lavendamycin have attracted special attention due to their broad biological activities
1–4
against bacteria, fungi, nematodes, viruses, and tumor cells.
Received 23 May 2011; accepted 18 August 2011.
We thank the DAAD (Deutscher Akademischer Austausch Dienst) for the award of a fellowship to J. E. Nycz.
The GAUSSIAN09 calculations were carried out at the Wrocław Centre for Networking and Supercomputing
(WCSS), Wrocław, Poland (http://www.wcss.wroc.pl, grant number 18).
Address correspondence to Jacek E. Nycz, Institute of Chemistry, University of Silesia, ul. Szkolna 9,
PL-40007 Katowice, Poland. E-mail: jnycz@us.edu.pl
5
64

REACTION OF QUINOLINE-5,8-DIONES WITH CHARGED PHOSPHORUS NUCLEOPHILES 565
O
O
MeO
H2N
MeO
H2N
O
O
N
CO2H
Me
N
CO2H
Me
N
N
O
O
H2N
HN
H2N
N
HO
MeO
OMe
Streptonigrin
2a
Lavendamycin
Scheme 1 Quinoline-5,8-dione (2a) as a common subunit for streptonigrin and lavendamycin.
Streptonigrin acts as a bioreductive agent, and is highly dependent on the interaction
with the transition metal ions Cu2 and Fe , and plays an important role in the production
+
2+
of free radicals through redox cycling of NAD(P)H. The antitumor activity of streptonigrin
2
+
2+
is accelerated by the transition metal ions Cu and Fe . Streptonigrin bonded to metal
5
ions has shown some full antibiotic and antitumor activities. The strong EPR (electron
paramagnetic resonance) signals upon reduction in the presence of metal ions indicated
5
the formation of metal–semiquinones. This process is inhibited by superoxide dismutase
5
and catalase. These results suggest that metal ions were directly involved in the action
of streptonigrin, in which the metal complexes of streptonigrin could be reduced to their
5
semiquinone forms by NADH for the cleavage of DNA. Wei et al. contradict the formation
3+
2+ 5
of a Fe –streptonigrin complex via simple reduction of streptonigrin by Fe .
So far, there has been no report about a phosphorylated quinoline-5,8-dione unit.
In consideration of the present knowledge of the reactivity of quinoline-5,8-diones, it is
anticipated that further investigations in this field may lead to new applications, not only in
the area of introducing a phosphorus-containing moiety.
RESULTS AND DISCUSSION
The phosphorylation of quinoline-5,8-diones, the structural building blocks of strep-
tonigrin or lavendamycin (Scheme 1), is still not fully explored. To increase accessibility,
the reactions between negatively charged phosphorus nucleophiles of the type R2P-YM
(
1a–d, Y = O or lone pair; R = Ph, tBu, OCH2CMe2CH2O, or EtO; M = Li or Na)
and 2a were chosen (Scheme 2). The conversion was unambiguous and gave exclusively
as electron transfer products the diphosphanes (diphosphane dioxides or hypophosphoric
acid esters) 6 together with the radical anion 3 with its characteristic deep green color.
The most likely mechanism to explain the origin of 6 is the dimerization of short-lived
phosphorus-centered radicals 5. The phosphorus-centered radicals, which have a lone
pair in the molecular plane and an unpaired electron perpendicular to the plane, such
·
6
as π-type radicals R2P , are expected to dimerize and form a P P bond, while this is
less obvious for σ-type species R2P( O) , in which the phosphorus atom is pyramidal.
·
The extent of pyramidalization of phosphorus in the radicals increases with increasing
6
,7
s-contribution. A common reactivity of P-centered radicals is the addition reaction to
6
double bonds. Kajiwara et al. confirmed that additions to electron poor double bonds
8
occurred faster than additions to electron rich double bonds. The assumed intermediates 5
dimerized and formed exclusively products with a P P bond in up to 88% yield (Scheme
9–14
ꢁ ꢁ
By allowing 1 to react with 2a, 1,1,2,2-tetraphenyldiphosphane-P,P -dioxide (6a )
2).
and 1,2-di-tbutyl-1,2-diphenyldiphosphane-1,2-dioxide (6b) (mixture of the meso and rac

5
66
J. E. NYCZ ET AL.
O
O
O
R
R
SET
THF
+
P
YM
+
P
Y
R'
R'
R"HN
N
Me
R"HN
N
Me
1
O-
5
M+
2
R" = H (a), COMe (b)
R" = H (3), COMe (4)
Yield of
R"
Y
Y
P
R
R
1
R
Ph
R'
Y
M
6
(%)
62*
88
1/2
P
a
b
c
Ph
Li
Li
H
H
H
H
R'
R'
6
Ph
tBu
OEt
O
O
O
O
OEt
Na
Na
Na
54
d
d
*
OCH CMe CH O
58
2
2
2
OCH CMe CH O
COMe 56
2
2
2
Isolated after oxidation to 6a' (6, R = R' = Ph, Y = O)
Scheme 2 Reaction of 1a–d with 2a and 2b.
ꢁ
ꢁ
isomers), as well as hypophosphoric acid tetraethyl ester (6d) and 5,5,5 ,5 -tetramethyl-
ꢁ
bis-(1,3,2)-dioxa-phosphinane-2,2 -dioxide (6e), were isolated among the final products.
The reaction of Ph2PLi (1a) with 2a in THF (tetrahydrofuran) yielded efficiently 1,1,2,2-
tetraphenyldiphosphane (6a). The 31P NMR spectrum showed only one resonance line
attributable to 6a (δ = −15.1 ppm). However, 6a were isolated after oxidation and the
ꢁ
poor solubility of 6a reduced the isolated yield. Similar reactivity was observed while
employing 2b. The reaction of 2b with 1 leads to the formation of the radical anion 4
with its characteristic pink color and to the formation of compound 6, possibly via 5. The
unresolved EPR spectra of 3 and 4 displayed an isotropic G value of 2.0039 and showed
a peak line width ꢀB = 7 G for 3 and ꢀB = 6 G for 4, which confirmed the existence of
semiquinone-type radical anions (Figure 1).
The phosphorus radicals 5 could not be detected by EPR in the reaction mixtures,
probably due to their short lifetimes. All presented charged nucleophiles 1a–d participated
15
16
in the single-electron transfer to 2a and 2b, as was postulated by Bunnett and Russell. In
that sense, the metal diorganophosphides behave similar to polarized metallated carbanions
(
organometallics).17 The in-situ generated radicals 5 do not undergo addition reactions to
2a or 2b (Scheme 2).
Recently, we presented the radical addition of neutral phosphorus nucleophiles to 2a
18
and 2b. They reacted in a similar fashion with the quinones 2a and 2b, giving exclusively
O(2)-phosphorylated products 8 in good yield (Scheme 3). We could not isolate or detect
reversed products, i.e., O(1) phosphorylation products, addition products to the acyl group,
or addition products to the activated C C bond (Michael-type products). Furthermore,
neither free radical intermediates nor radical coupling products with a P P bond such
as diphosphanes, diphosphane dioxides, or hypophosphoric acid esters were detected in
these reactions. This strongly suggests that the process occurred without the formation of
completely free radical species.
At first glance, the mechanisms of the reactions between charged and neutral phos-
phorus nucleophiles 1 with 2a and 2b (Scheme 3) are different. However, in both cases,
electron transfer processes (SET) from the phosphorus nucleophile 1 to 2a and 2b take
place. We identified 3, 4, and 8 as the reduction products of 2a and 2b. For both pathways,

REACTION OF QUINOLINE-5,8-DIONES WITH CHARGED PHOSPHORUS NUCLEOPHILES 567
Y
R
R
base
P
M
P
YM
R'
R'
1
1
Previous work 2a or 2b
This work 2a or 2b
SET
SET
O
O
R
+
P
Y
R
R'
P
YM
R"HN
N
Me
R"HN
N
Me
R'
O-
O-
5
M+
R" = H (3), COMe (4)
7
Y
Y
OH
R
R
1
/2
P
P
R'
R'
6
R"HN
N
Me
O
R
M = Li, Na, SiMe or H
Y = O or lone pair
P
8
3
R'
O
R = Ph, tBu, OEt, OiPr or OMe; R' = Ph, OEt, OiPr; R, R' = OCH CMe CH O; R" = H or COMe
2
2
2
Scheme 3 Proposed mechanism of the reaction between the phosphorus nucleophiles 1 and 2a or 2b.
Figure 1 EPR spectra of solutions of radical anions 3 (left) and 4 (right) in THF at 293 K.

5
68
J. E. NYCZ ET AL.
Figure 2 Calculated natural charges for 2a (left) and 2b (right).
we do not observe standard addition products to the P C bond. This could be explained by
our computational studies, which show the highest electron density at C6 for both molecules
2
a and 2b (Figure 2). This prevents a Michael addition. The dimerization of radical ion
1
9,20
pair 7 possibly occurs because of electrostatic interaction and/or hydrogen bonding
and some other contact interaction. Fukuzumi et al. demonstrated that a variety of metal
2
1,22
ions significantly accelerate electron transfer reactions of carbonyl compounds.
The
+
+
role of the metal ion (Li or Na ) in the interaction of 3 or 4 with radical 5 has not yet
been fully understood, and the metal binding mode as well as the structure of these metal
complexes could not be definitely determined in our studies. The crystallization of 3 and 4
is in progress. In the literature, there are some examples reported similar to our oxidative
P P coupling. Shulyupin et al. observed fast redox P P coupling (with 100% yield) during
the addition of Ph2P H to olefins in the presence of Ni(II) complexes. The dimerization
was also observed as a side reaction for Ni(0) complexes. Nief and Mathey, in order to
avoid a similar redox P P coupling in the reaction of a lithium phospholide with MCl4,
23
23
24
used the tin or lead derivatives of phospholes.
Cyclic voltammetry studies showed similar redox properties for both 2a and 2b.18,25
The first reduction potential corresponds to the electrochemical behavior of natural occur-
ring quinones.1 Therefore, it highlights the possible role of electron transfer mechanism
in the biological activities of naturally occurring quinolinediones, such as lavendamycin or
streptonigrin.
8,26
The calculated potential values in this study could explain not only the selectivity of
phosphorylation18 but also the complexation properties of 2b (Figure 2).
Tautomeric forms of 2a also suggest the acidic properties of the proton located at C6
25
(
Scheme 4).
Doyle et al.27 observed an exchange of the proton at C6 ( H NMR signal at 5.91) in
1
1
the H NMR spectrum of lavendamycin recorded in CF3CO2D.
O
O
OH
O
H
H
H
H
H N
N
Me
HN
N
Me
HN
N
Me
2
O
O
Scheme 4 Tautomeric forms of 2a.

REACTION OF QUINOLINE-5,8-DIONES WITH CHARGED PHOSPHORUS NUCLEOPHILES 569
CONCLUSION
This study describes the electron transfer properties of the structurally characterized
compounds 2a and 2b. All employed charged phosphorus nucleophiles 1a–d participated
in electron transfer to 2a or 2b, producing the very stable EPR-active radical anions 3 and
4
, respectively, as well as the probably phosphorus-centered radicals 5. The intermediates 5
ꢁ
ꢁ
dimerized, forming P P bonds to yield 1,1,2,2-tetraphenyldiphosphane-P,P -dioxide (6a ),
,2-di-tert-butyl-1,2-diphenyldiphosphane (6b), compound 6c as mixture of the meso and
1
ꢁ
ꢁ
rac isomer, hypophosphoric acid tetraethyl ester (6d), and 5,5,5 ,5 -tetramethyl-bis-(1,3,2)-
dioxaphosphinane-2,2 -dioxide (6e). No products indicating further interactions of radicals
ꢁ
5
with 2a or 2b were observed in all the reactions investigated.
EXPERIMENTAL PART
All experiments were carried out in an atmosphere of dry argon, using Schlenk tech-
niques. Solvents were processed by common drying (benzene and THF over benzophenone
ketyl, CHCl3 and CH2Cl2 over P2O5, hexane over sodium–potassium alloy), distillation,
and degassing. Chromatography was carried out on silica gel 60 (0.15–0.3 mm, Machery-
Nagel). NMR spectra were obtained with a Bruker Avance 400 instrument operating at
1
31
13
◦
4
00.13 MHz ( H), 161.9 MHz ( P), and 100.4 MHz ( C) at 30 C; chemical shifts are
1
13
31
referenced to external TMS ( H, C), 85% H3PO4 (ꢁ = 40.480747MHz, P); positive
signs of chemical shifts denote shifts to lower field; coupling constants are given as ab-
solute values. EPR spectra were recorded in the X band with a Bruker System ESP 300
instrument. Elemental analysis: Perkin-Elmer 2400CHSN/O Analyzer. Mass spectra were
obtained with a MASPEC II system [II32/99D9], a Varian MAT 711, and a Finnigan MAT
95 (Finnigan MAT GmbH); in EI (electron ionization) mode (70 eV) and, where necessary,
liquid SIMS (secondary ion mass spectrometry) technique was applied. Melting points were
measured in sealed capillaries and are uncorrected. Compounds 2a and 2b were synthesized
18
according to procedures described in the literature.
Reaction of 1a and 1b with 2a
n-BuLi (2.2 mL, 2.5 M solution in hexane) was slowly added to diphenyl phosphine
◦
(
1a) or tert-butyl phenyl phosphine oxide (1b) (5 mmol) in THF (20 mL) solution at −78 C.
◦
The reaction mixture was stirred for 1 h at −78 C. Subsequently, 2a (5 mmol) in THF
(
100 mL) was added. After 3 h at room temperature (r.t.), a sample of the reaction mixture
was investigated by NMR and EPR spectroscopy. Subsequently, in the case of the reaction
with 1a, dry air was passed through the reaction mixture. Then, the reaction mixture was
washed with aqueous KHSO4 solution (2 × 25 mL). The water layer was extracted with
CH2Cl2 and the combined organic phase was dried over MgSO4. After solvent evaporation,
the products were purified by crystallization and chromatography.
ꢀ
ꢀ 13,14
Tetraphenyldiphosphane-P,P -dioxide (6a )
◦
1
Yield 0.623 g (1.5 mmol, 62%), m.p. = 168–169 C; H NMR (400.13 MHz,
◦
CDCl3/DMSO-d6, 30 C): δ = 6.90–6.99 (m, 6H, arom-H) 7.81–7.85 (m, 4H, arom-
31
1
◦
H), P{ H} NMR (161.9 MHz, DMSO-d6, 30 C): δ = 24.9; Elemental analysis: Found
C, 69.67; H, 5.27; C24H20O2P2 requires C, 71.64; H, 5.01%.

5
70
J. E. NYCZ ET AL.
1,2-Di-tert-butyl-1,2-diphenyldiphosphane-1,2-dioxide (6b) and (6c)
1
3,14
Mixture of meso and rac form
; CHCl3:MeOH = 50:1; yield 0.796 g (2.2 mmol,
3
◦
1
◦
8
1
3
8%; 6b (meso): m.p. = 205 C, H NMR (400.13 MHz, CDCl3, 30 C): δ = 0.98 (d, JPH =
31 1
6 Hz, 18H, tBu), 7.40–8.45 (m, 10H, arom-H); P{ H} NMR (161.9 MHz, CDCl3,
◦
+
◦
1
0 C): δ = 39.8; MS (SIMS): M 362; 6c (rac): m.p. = 192–193 C; H NMR (400.13
◦
3
MHz, CDCl3, 30 C): δ = 1.38 (d, JPH = 17 Hz, 18H, tBu), 7.00–7.80 (m, 10H, arom-H);
31
1
◦
+
P{ H} NMR (161.9 MHz, CDCl3, 30 C): δ = 50.7; MS (SIMS): M 362; Elemental
analysis: Found C, 63.17; H, 7.95; C20H28O2P2 · H2O requires C, 63.15; H, 7.95%.
Reaction of 1c and 1d with 2a
Diethyl phosphonate (1c) or 5,5-dimethyl-(1,3,2)-dioxaphosphinane-2-oxide (1d)
(
5 mmol) was added to an NaH suspension (0.132 g, 5.5 mmol) in THF (20 mL) at
r.t. and the reaction mixture was stirred until the evolution of H2 was complete. Then, 2a
5 mmol) in THF (100 mL) was added. After 3 h at r.t., a sample of the reaction mixture
(
was investigated by NMR and EPR spectroscopy. The reaction mixture was washed with
aqueous KHSO4 solution (2 × 25 mL), the water layer was extracted with CH2Cl2, and the
organic phase was dried over MgSO4. After evaporation of the CH2Cl2, the products were
purified by crystallization and chromatography.
Hypodiphosphoric Acid Tetraethyl Ester (6c)
◦
1
Yield 0.369 g (1.3 mmol, 54%); m.p. = 168–169 C; H NMR (400.13 MHz, DMSO-
◦
d6, 30 C): δ = 1.18 (t, JHH = 7 Hz, 12H, CH3), 4.23 (m, 4H, CH2), 4.33 (m, 4H, CH2);
3
1
1
◦
P{ H} NMR (161.9 MHz, DMSO-d6, 30 C): δ = −2.0; Elemental analysis: Found C,
1
3
3.89; H, 7.50; C8H20O2P2 · 2 H2O requires C, 33.93; H, 7.47%.
ꢀ ꢀ ꢀ
,5,5 ,5 -Tetramethyl-bis-(1,3,2)-dioxaphosphinane-2,2 -dioxide (6e)
13,14
5
◦
1
From diethyl ether, yield 0.432 g (1.4 mmol, 58%); m.p. = 248–249 C; H NMR
◦
(
1
(
400.13 MHz, CDCl3, 30 C): δ = 0.90 (s, 6H, CH3), 1.36 (s, 6H, CH3), 3.97 (dd, JHH =
3
1
1
0.6 Hz, JPH = 22.2 Hz, 4H, CH), 4.68 (d, JHH = 10.6 Hz, 4H, CH); P{ H} NMR
◦
161.9 MHz, CDCl3, 30 C): δ = −0.68; Elemental analysis: Found C, 39.92; H, 7.05;
C10H20O6P2 requires C, 40.28; H, 6.76%.
Reaction of 1d with 2b
Diethyl phosphonate (1d) (5 mmol) was added to an NaH (0.132 g, 5.5 mmol)
suspension in THF (20 mL) at r.t. and the reaction mixture was stirred until evolution of H2
ceased. Subsequently, 2b (5 mmol) in THF (100 mL) was added. After 3 h at r.t., a sample
of the reaction mixture was investigated by NMR and EPR spectroscopy. The reaction
mixture was washed with aqueous KHSO4 solution (2 × 25 mL) and the water layer was
extracted with CH2Cl2. The organic phase was dried over MgSO4. After evaporation of
ꢁ
ꢁ
the CH2Cl2, the products were purified by crystallization and chromatography: 5,5,5 ,5 -
ꢁ
13,14
Tetramethyl-bis-(1,3,2)-dioxaphosphinane-2,2 -dioxide (6e)
.835 g (1.4 mmol, 56%).
(from diethyl ether): yield
0

REACTION OF QUINOLINE-5,8-DIONES WITH CHARGED PHOSPHORUS NUCLEOPHILES 571
Synthesis of Compounds 3 and 4
Method A: n-BuLi (2.2 mL, 2.5 M solution in hexane) was slowly added to diphenyl
phosphine (1a) or tert-butylphenylphosphinic oxide (1b) (5 mmol) in THF (20 mL) at
◦
◦
−
78 C. The reaction mixture was stirred for 1 h at −78 C. Subsequently, 2a (5 mmol) in
THF (100 mL) was added. After evaporation of the solvent, compound 3 was purified by
crystallization.
Method B: Diethyl phosphonate (1d) (5 mmol) was added to a suspension of NaH
(0.132 g, 5.5 mmol) in THF (20 mL) at r.t. and the reaction mixture was stirred until
evolution of H2 ceased. Subsequently, 2b (5 mmol) in THF (100 mL) was added. After
evaporation of the solvent, compound 4 was purified by crystallization.
Method C: Into freshly prepared potassium anthracenide (5 mmol) in 25 mL of THF
◦
at −78 C, generated from anthracene (0.891g, 5 mmol) and potassium (0.195g, 5 mmol),
2
a or 2b (5 mmol) in THF (100 mL) was added. The reaction mixture was stirred until
◦
the disappearance of the blue color. After 3 h at −78 C, a sample of the reaction mixture
was investigated by EPR spectroscopy. After evaporation of the solvent, the products were
purified by crystallization.
Crystallization of 3 and 4
The growth of crystals suitable for single-crystal X-ray diffraction was attempted by
◦
slow evaporation of the solvent at r.t., as well as from the solution at −35 C. Crystallization
of compounds 3 and 4 is a work in progress.
DFT Calculations
The calculations were carried out using the Gaussian0928 program. The DFT/
B3LYP29 method was used for the geometry optimization with the 6-31G basis set
∗∗
used for all atoms in calculations.
REFERENCES
1
2
3
4
. Take, Y.; Kubo, T.; Takemori, E.; Inouye, Y.; Nakamura, S.; Nishimura, T.; Suzuki, H.;
Yamaguchi, H. J. Antibiot. 1989, 42, 968-976.
. Balitz, D. M.; Bush, J. A.; Bradner, W. T.; Doyle, T. W.; O’Herron, F. A.; Nettleton, D. E.
J. Antibiot. 1982, 35, 259-265.
. Behforouz, M.; Cai, W.; Stocksdale, M. G.; Lucas, J. S.; Jung, J. Y.; Briere, D.; Wang, A.; Katen,
K. S.; Behforouz, N. C. J. Med. Chem. 2003, 46, 5773-5780.
. Boger, D. L.; Yasuda, M.; Mitscher, L. A.; Drake, S. D.; Kitos, P. A.; Thompson, S. C. J. Med.
Chem. 1987, 30, 1918-1928.
5
6
7
8
. Wei, X.; Ming, L.-J. J. Chem. Soc., Dalton Trans. 1998, 2793-2798.
. Marque, S.; Tordo, P. Top. Curr. Chem. 2005, 250, 43-76.
. Leca, D.; Fensterbank, L.; Lac oˆ te, E.; Malacria, M. Chem. Soc. Rev. 2005, 34, 858-865.
. Kajiwara, A.; Konishi, Y.; Morishima, Y.; Schnabel, W.; Kuwata, K.; Kamachi, M. Macro-
molecules 1993, 26, 1656-1658.
9. Hitchcock, P. B.; Lappert, M. F.; Nycz, J. E. Chem. Commun. 2003, 1142-1143.
1
1
0. Bezombes, J.-P.; Hitchcock, P. B.; Lappert, M. F.; Nycz, J. E. Dalton Trans. 2004, 499-501.
1. Bezombes, J.-P.; Borisen, K. B.; Hitchcock, P. B.; Lappert, M. F.; Nycz, J. E.; Rankin, D. W. H.;
Robertson, H. E. Dalton Trans. 2004, 1980-1988.

5
72
J. E. NYCZ ET AL.
1
1
1
1
1
1
1
2. Nycz, J. E. Polish J. Chem. 2009, 83, 1323-1328.
3. Nycz, J. E.; Musiol, R. Heteroatom Chem. 2006, 17, 310-316.
4. Nycz, J. E. Heteroatom Chem. 2008, 19, 234-237.
5. Bunnett, J. F. Acc. Chem. Res. 1978, 11, 413-420.
6. Russell, G. A.; Hershberger, J. J. Chem. Soc. Chem. Commun. 1980, 216-217.
7. Kaim, W. Acc. Chem. Res. 1985, 18, 160-166.
8. Nycz, J. E.; Malecki, G.; Ponikiewski, L.; Leboschka, M.; Nowak, M.; Kusz, J. J. Mol. Struct.
2
011, 986, 39-48.
9. Fukuzumi, S.; Okamoto, K.; Yoshida, Y.; Imahori, H.; Araki, Y.; Ito, O. J. Am. Chem. Soc. 2003,
25, 1007-1013.
0. Kaupp, M.; Remenyi, C.; Vaara, J.; Malkina, O. L.; Malkin, V. G. J. Am. Chem. Soc. 2002, 124,
709-2722.
1
2
1
2
21. Yuasa, J.; Suenobu, T.; Fukuzumi, S. J. Am. Chem. Soc. 2003, 125, 12090-12091.
22. Fukuzumi, S.; Ohkubo, K.; Okamoto, T. J. Am. Chem. Soc. 2002, 124, 14147-14155.
23. Shulyupin, M. O.; Kazankova, M. A.; Beletskaya, I. P. Org. Lett. 2002, 4, 761-763.
24. Nief, F.; Mathey, F. J. Chem. Soc. Chem. Commun. 1988, 770-771.
25. Paretzki, A.; Das, H. S.; Weisser, F.; Scherer, T.; Bubrin, D.; Fiedler, J.; Nycz, J. E.; Sarkar, B.
Eur. J. Inorg. Chem. 2011, 2413-2421.
2
2
2
6. Nycz, J. E.; Malecki, G.; Morag, M.; Nowak, G.; Ponikiewski, L.; Kusz, J.; Switlicka, A. J. Mol.
Struct. 2010, 980, 13-17.
7. Doyle, T. W.; Balitz, D. M.; Grulich, R. E.; Nettleton, D. E. Tetrahedron Lett. 1981, 22, 4595-
4598.
8. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;
Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.;
Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.;
Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.;
Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers,
E.; Kudin, K. N.: Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell,
A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.;
Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.;
Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma,
K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.;
Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision A.1,
Gaussian Inc.: Wallingford, CT, 2009.
29. Becke, A. D. J. Chem. Phys. 1993, 98, 5648-5652.