Preparation of sila-functional 3-sila-1-thiacyclohexanes

Article abstract of DOI:10.1016/j.jorganchem.2009.11.038

First sila-functional heterocycles 7 and 9 with Si and S atoms in 1,3-position bearing the reactive X group at silicon (X = i-PrO, F) were readily prepared from the corresponding phenyl-protected cycle 6 in good yields via Ph-Si bond cleavage by electroph

Full text of DOI:10.1016/j.jorganchem.2009.11.038

Journal of Organometallic Chemistry 695 (2010) 663–666
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Preparation of sila-functional 3-sila-1-thiacyclohexanes
*
Svetlana V. Kirpichenko , Aleksander I. Albanov
Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 25 April 2009
Received in revised form 7 July 2009
Accepted 26 November 2009
Available online 2 December 2009
First sila-functional heterocycles 7 and 9 with Si and S atoms in 1,3-position bearing the reactive X group
at silicon (X = i-PrO, F) were readily prepared from the corresponding phenyl-protected cycle 6 in good
yields via Ph–Si bond cleavage by electrophilic reagents. Treatment of i-propoxy derivative 7 with LiAlH4
gave heterocycle 8 with Si–H bond.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Silicon
Silathiacyclohexanes
Synthesis
Protecting group
1. Introduction
9 via a common approach from (chloromethyl)methylallylfluoros-
ilane. The latter was prepared from commercially available (chlo-
Over many years there has been a considerable interest in sil-
athiacycloalkanes, organosilicon heterocyclic compounds contain-
ing the Si–(CH2)n–S (n = 1–3) moiety [1]. Most significant results
in this field including some of our own results are given in recent
review [1a]. Due to the presence of both elements these com-
pounds exhibit the peculiar and complementary reactivity. To date,
all researches have focused on the chemistry of 1,3 or 1,4-silathia-
cyclohexanes bearing simple alkyl groups at the silicon atom [1a].
Previously we have studied their S-functionalization including
conversions into sulfoxides [2a,b], sulfones [2a] and sulfimines
[2c,d]. Along the line of our studies, we became interested in a
new type of 1,3-silathiacyclohexanes having a labile Si–X bond
(X – hydrogen, halogen, etc). They offer many opportunities for
nucleophilic substitution reactions at the silicon atom and are
the interesting objects for conformational analysis. Several routes
to 1,3-silathiacycloalkanes with different ring size are available
[1a], with the most recent one involving the photochemical addi-
tion of thioacetic acid to dimethyl(chloromethyl)allyl or vinylsil-
anes followed by solvolysis of the thioacetate adducts and ring
forming stage [2a,3a,b]. The considerable drawback of this method
for preparation of related sila-functional 3-sila-1-thiacyclohexanes
appears to be difficult preparation of the starting silanes. Besides,
the presence of a labile functional group such as RO, Si–H or Si–F
in the intermediate thioacetates complicates their purification
and subsequent transformations under basic conditions. Recently
we tried to synthesize 3-fluoro-3-methyl-3-sila-1-thiacyclohexane
romethyl)methyldichlorosilane in low overall yield in the two
steps [4]. Although the target thioacetate was formed in high yield
(78%), its solvolysis was problematic due to sensitivity of the Si–F
bond to bases. As a mild base, pyrrolidine was proposed for cleav-
age of thioacetates [5]. Indeed, reaction of 3-[(chloromethyl)meth-
ylfluorosilyl]propylthioacetate with pyrrolidine in acetonitrile
gave desired heterocycle 9, however, in low isolated yield (10%)
[6].
Therefore, we chose an alternative protection protocol for such
substrates which involves the preparation of precursor stable to
synthetic procedure and purification techniques. In organosilicon
chemistry one of the most exploited protecting groups is an aryl
moiety, especially in synthesis of silanols and silanediols. Removal
of the protecting groups by electrophilic reagents allows to remain
other Si–C bonds intact [7,8].
Here we described a simple and versatile route to the first 3-
sila-1-thiacyclohexanes with reactive X–Si groups based on Si–
C(Ph) bond cleavage of phenyl-protected heterocycle 6.
2. Results and discussion
Cyclic compound 6 was prepared in four-step synthesis accord-
ing to Scheme 1. Thus, treatment of starting (chloromethyl)meth-
yldichlorosilane with phenylmagnesium bromide afforded silane
1 the reaction of which with allylmagnesium chloride resulted in
allylsilane 2.
After vacuum distillation of a poor separable mixture of 2 and 3,
their ratio of 94%:6% was achieved. This mixture was subjected to
the addition of thioacetic acid to give thioacetates 4 and 5 sepa-
* Corresponding author. Tel.: +7 3952 426345; fax: +7 3952 419346.
E-mail address: svk@irioch.irk.ru (S.V. Kirpichenko).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.11.038

664
S.V. Kirpichenko, A.I. Albanov / Journal of Organometallic Chemistry 695 (2010) 663–666
CH2Cl
PhMgBr
AllCl/Mg
(ClCH2)MePhSiCl
(ClCH2)MeSiCl2
MePhSi
+
Me2PhSiCH2CH=CH2
1
3
CH2CH=CH2
2
CH3COSH/hν
CH2Cl
+
Me2PhSi(CH2)3SCOCH3
MePhSi
5
(CH2)3SCOCH3
4
MeONa/MeOH
Me
Ph
Si
S
6
Scheme 1.
rated by column chromatography. Methanolysis of thioacetate 4
followed by the intramolecular ring closure provided phenyl-pro-
tected cycle 6 in high yield (74%).
sodium benzophenone ketyl prior to use; n-pentane, CH2Cl2, i-pro-
panol, triethylamine were distilled from CaH2. Analytical thin layer
chromatography and column chromatography were carried out
using silica gel plates (60 F-254, Merck) and silica gel 60 (0.063–
0.200 mm, ICN Biomedical Inc.), respectively. The 1H, 13C, 19F and
29Si NMR spectra were recorded on Bruker DPX-400 spectrometer
(1H, 400.1 MHz; 13C, 100.6 MHz; 19F, 376.5 MHz; 29Si, 79.5 MHz).
Chemical shifts (ppm) were determined relative to residual CHCl3
By the action of triflic acid arylsilanes are readily converted into
the highly reactive silyl triflates [9] which are useful for further
transformations into Si–halogen [10], Si–H [11] and Si–OR
[10b,11b] derivatives. In fact, removal of the phenyl group from
6 with triflic acid and subsequent treatment with i-propanol/tri-
ethylamine gave 7 in good yield (53%). The resulting compound
was reduced with lithium aluminum hydride to generate heterocy-
clic compound 8 with Si–H bond (Scheme 2).
Replacing phenyl group with fluoride can easily be accom-
plished by treatment with triflic acid/fluorinating agent (HF [12],
NaF [10c]). One-step conversion of the Ph–Si bond into a F–Si moi-
ety with use of boron trifluoride-acetic acid complex seems to be
more attractive procedure [13]. Reaction of this complex with 6
under mild conditions was successful, producing desired fluoro
containing cycle 9 in 35% isolated yield.
(1H, d 7.27, CDCl3), internal CDCl3
CFCl3
(
13C, d 77.0, CDCl3), external
(
19F, d 0.00, CDCl3), and external TMS (29Si, d 0.00, CDCl3).
Analysis and assignment of the 1H NMR data were supported by
homonuclear (COSY) and heteronuclear (HSQC 13C–1H, HMBC
13C–1H) 2D correlation experiments.
3.2. Synthesis of compounds 1–9
3.2.1. (Chloromethyl)methylphenylchlorosilane (1)
(Chloromethyl)methylphenylchlorosilane (1) was synthesized
following the general procedure described in Ref. [14]. Phenylmag-
nesium bromide, prepared from bromobenzene (39.26 g, 0.25 mol)
and powder magnesium (7.20 g, 0.30 g-a) in Et2O (100 mL), was
added to (chloromethyl)methyldichlorosilane (45.79 g, 0.28 mol)
in Et2O (50 mL). The mixture was refluxed 6 h, cooled, diluted with
hexane (100 mL) and filtered. Concentration in vacuo followed by
rapid distillation from the remaining magnesium salts afforded a
liquid product (31.01 g, b.p. 80–123 °C/3 mm Hg) which was redis-
tilled to give 1 (27.14 g, 0.13 mol, 53%), b.p. 78–82 °C/2 mm Hg.
Lit.: [12]: b.p. 106–108 °C/8 mm Hg. 1H NMR (CDCl3): d 0.87 (s,
3H, Me), 3.18 (s, 2H, CH2Cl), 7.45–7.54 (m, 3H, Hm+p), 7.72 (m,
2H, Ho). 13C NMR (CDCl3): d À1.65 (Me), 29.78 (CH2Cl), 128.23
(Cm), 131.11 (Cp), 133.64 (Co), 133.91 (Ci). 29Si NMR (CDCl3): d
11.91.
Compounds 7–9 were isolated as colorless liquids, whereas cy-
cle 6 was obtained as a clear oil slowly crystallizing on keeping.
Compounds 2–9 are stable to a wide range of workup, reaction
conditions and purification by column chromatography on silica
gel (except compound 7) and can be handled without any
precautions.
In conclusion, the above reactions offer the preparative route
approach to a wide variety of new types of sila-functional hetero-
cycles, useful for studies of their reactivity and conformational
behavior. These two aspects are under current investigations.
3. Experimental
3.1. General comments
All reactions were carried out under an argon atmosphere with
magnetic stirring. Triflic acid was purchased from Alfa Aesar and
used without further purification. Diethyl ether was distilled from
3.2.2. (Chloromethyl)allylmethylphenylsilane (2)
(Chloromethyl)allylmethylphenylsilane (2) was prepared by a
modified procedure [15]. (Chloromethyl)methylphenylchlorosi-
lane (1) (25.10 g, 0.12 mol) in Et2O (40 mL) was added to a vigor-
ously stirred Grignard reagent, prepared from allyl chloride
(13.01 g, 0.17 mol), magnesium powder (4.09 g, 0.17 g-a) in Et2O
(20 mL) at 0 °C. The reaction mixture was then refluxed for 6 h.
Hexane (40 mL) was added before quenching with a saturated
aqueous NH4Cl solution at 0 °C. The layers were separated and
the aqueous layer was extracted with Et2O (2 Â 20 mL). The com-
bined organic phase was dried (MgSO4), filtered and concentrated
under reduced pressure to give the crude product (17.95 g) con-
taining allylsilanes 2 and 3 in a 9:1 ratio (by 1H NMR data). Vacuum
distillation gave 3 (1.27 g, 0.7% yield, 90% purity by 1H NMR, b.p.
1. TfOH
LiAlH4
Me
Me
H
Si
Si
S
S
Si
S
2. i-PrOH/Et3N
i-PrO
8
7
9
Me
Ph
Si
S
6
.
BF3 2AcOH
Me
F
Scheme 2.

S.V. Kirpichenko, A.I. Albanov / Journal of Organometallic Chemistry 695 (2010) 663–666
665
76–77 °C/1 mm Hg) and target allylsilane 2 (15.33 g, 43% yield, 94%
purity by 1H NMR), b.p. 87–88 °C/1 mm Hg used without further
purification in the next step.
Analytically pure samples of 2 and 3 were obtained by column
chromatography (silica gel, hexane).
CCHBC), 2.57 (m, 2H, CCH2S), 7.39 (m, 3H, Hm+p), 7.57 (m, 2H, Ho).
13C NMR (CDCl3): d À4.86 (MeSi), 12.69 (SiCH2C), 13.40 (SiCH2S),
26.99 (CCH2C), 32.30 (CCH2S), 127.93 (Co), 129.38 (Cp), 133.65
(Cm), 137.72 (Ci). 29Si NMR (CDCl3): d À16.23. Anal. Calc. for
C11H16SiS: C, 63.40; H, 7.74; Si, 13.48. Found: C, 62.99; H, 7.45;
Si, 13.10%.
Data for 2: a colorless oil, Rf = 0.54 (hexane). 1H NMR (CDCl3): d
0.43 (s, 3H, MeSi), 1.94 (ddt, 1H, JAB = 13.8, J = 8.2 and J = 1.3 Hz, Si-
CHAC), 1.98 (ddt, 1H, SiCHBC), 3.00 (d, 1H, JAB = 13.8 Hz, SiCHACl),
3.09 (d, 1H, SiCHBCl), 4.93 (ddt, 1H, cisJ = 9.9, J = 1.8 and J = 1.3 Hz,
@CHA), 4.97 (ddt, 1H, transJ = 16,9 Hz, @CHB), 5.81 (ddt, 1H, CH@),
7.41 (m, 3H, Hm+p), 7.56 (m, 2H, Ho). 13C NMR (CDCl3): d À6.56
(MeSi), 20.16 (SiCH2C), 28.58 (SiCH2Cl), 114.72 (@CH2), 128.03
(Cm), 129.89 (Cp), 133.21 (CH@), 134.07 (Co), 134.59 (Ci). 29Si
NMR (CDCl3): d À4.97. Anal. Calc. for C11H15SiCl: C, 62.68; H,
7.17; Si, 13.33. Found: C, 62.88; H, 7.27; Si, 13.24%.
3.2.5. 3-i-Propoxy-3-methyl-3-sila-1-thiacyclohexane (7)
Triflic acid (1.90 mL, 22.0 mmol) was added dropwise to a stir-
red solution of 6 (4.00 g, 19.2 mmol) in n-pentane (10 mL) at room
temperature, and the mixture was then heated under reflux for 1 h.
After cooling a mixture of i-propanol (1.38 g, 23.0 mmol) and tri-
ethylamine (2.33 g, 23.0 mmol) was added at 0 °C. After 10 min.,
the reaction mixture was warmed to room temperature and stirred
further for 2 h. The upper organic phase was separated, and the
lower phase was washed with n-pentane (2 Â 10 mL). The organic
phases were combined, the solvent was removed by distillation
under atmospheric pressure, and the residue was distilled in vacuo
to give 7 in 53% yield (1.92 g) as a colorless liquid, b.p. 95–96 °C/
14 mm Hg.
Data for 3: a colorless oil, Rf = 0.34 (hexane). 1H NMR (CDCl3): d
0.37 (s, 6H, MeSi), 1.84 (dt, 2H, J = 8.2 and J = 1.9 Hz, SiCH2C), 4.93
(ddt, 1H, cisJ = 10.1, J = 2.1 and J = 1.3 Hz, @CHA), 4.95 (ddt, 1H,
transJ = 16.8 Hz, @CHB), 5.86 (ddt, 1H, CH@), 7.43 (m, 3H, Hm+p),
7.60 (m, 2H, Ho). 13C NMR (CDCl3): d À3.51 (MeSi), 23.66 (SiCH2C),
113.38 (@CH2), 127.72 (Cm), 128.97 (Cp), 133.55 (Co), 134.57 (CH@),
138.61 (Ci). 29Si NMR (CDCl3): d À4.59. The 1H and 13C NMR data
are consistent with those reported in Ref. [16].
Data for 7: 1H NMR (CDCl3): d 0.28 (s, 3H, MeSi), 0.73 (ddd, 1H,
JAB = 14.55, J = 11.37, J = 4.77 Hz, SiCHAC), 0.80 (m, 1H, SiCHBC),
1.15 (d, 6H, Me2CHO, J = 6.11 Hz), 1.60 (d, 1H, JAB = 14.43 Hz, Si-
CHAS), 1.93 (d, 1H, SiCHBS), 1.92 (m, 1H, CCHAC), 2.25 (m, 1H,
CCHBC), 2.43 (m, 2H, CCH2S), 4.05 (heptet, 1H, CHO). 13C NMR
(CDCl3): d À2.76 (MeSi), 15.82 (SiCH2C), 16.27 (SiCH2S), 27.16 (Me-
CHO), 30.07 (CCH2C), 33.53 (CCH2S), 66.58 (CHO). 29Si NMR
(CDCl3): d À1.64. Anal. Calc. for C8H18Si0S: C, 50.57; H, 9.54; Si,
14.75. Found: C, 50.38; H, 9.58; Si, 14.75%.
3.2.3. 3-[(Chloromethyl)methylphenylsilyl]propylthioacetate (4)
Freshly distilled thioacetic acid (1.01 g, 1.0 mL, 13.2 mmol) was
added dropwise to allylsilane 2 (1.86 g, 8.8 mmol, containing 6% of
3) and irradiated for 3 h using a DRT-400 mercury lamp. The reac-
tion temperature was maintained at 40 °C. Excess of thioacetic acid
was removed under reduced pressure and the crude product
(2.24 g) was purified by column chromatography (silica gel, hex-
ane-ether, increasing polarity from 25:1 to 9:1) gave 4 (1.69 g,
67%) and 5 (0.15 g).
3.2.6. 3-Methyl-3-sila-1-thiacyclohexane (8)
Compound 7 (1.92 g, 10.1 mmol) was added to a stirred suspen-
sion of lithium aluminum hydride (0.3 g, 7.1 mmol) in diethyl
ether (5 mL) at room temperature. The resulting mixture was
heated under reflux for 4 h and allowed to cool to room tempera-
ture. After adding pentane (10 mL) the reaction mixture was added
to a stirred mixture of concentrated hydrochloric acid (25 mL), n-
pentane (20 mL), water (25 mL) and ice (30 g). The organic layer
was separated and the aqueous phase was extracted with pentane
(2 Â 10 mL). The combined organic extracts were dried over
MgSO4. The solvents were removed under atmospheric pressure
to give the crude product 8 (1.27 g), vacuum distillation of which
afforded compound 8 (0.55 g, 41% yield).
Data for 4: a colorless oil, Rf = 0.32 (silica gel, hexane/ether, 9:1).
1H NMR (CDCl3): d 0.41 (s, 3H, MeSi), 1.01 (m, 2H, SiCH2C), 1.64 (m,
2H, CCH2C), 2.31 (s, 3H, CH3CO), 2.87 (t, 2H, J 7.17 Hz, CH2S), 2.97
(d, 1H, JAB = 14.08 Hz, SiCHACl,), 3.03 (d, 1H, SiCHBCl) 7.39 (m, 3H,
Hm+p), 7.51 (m, 2H, Ho). 13C NMR (CDCl3): d À6.40 (MeSi), 12.03
(SiCH2C), 23.95 (CCH2C), 28.99 (CH2Cl), 30.64 (CH3CO), 32.28
(CCH2S), 128.03 (Cm), 129.79 (Cp), 133.87 (Co), 134.73 (Ci), 195.80
(CO). 29Si NMR (CDCl3): d À2.92. Anal. Calc. for C13H19SiClOS: C,
54.43; H, 6.68; Si, 9.79. Found: C 54.54; H 6.50; Si 9.82%.
Data for 5: a colorless oil, Rf = 0.57 (hexane/ether, 9:1). 1H NMR
(CDCl3): d 0.35 (s, 6H, Me2Si), 0.90 (m, 2H, SiCH2), 1.66 (m, 2H,
CCH2C), 2.36 (s, 3H, CH3CO), 2.94 (t, 2H, J = 7.3 Hz, SCH2), 7.42
(m, 3H, Hm+p), 7.56 (m, 2H, Ho). 13C NMR (CDCl3): d À3.10 (MeSi),
15.41 (SiCH2C), 24.42 (CCH2C), 30.62 (CH3CO), 32.51 (CCH2S),
127.81 (Co), 128.97 (Cp), 133.53 (Cm), 138.85 (Ci), 195.79 (C@O).
29Si NMR (CDCl3): d À2.98.
The crude product can be also purified by column chromatogra-
phy on silica gel using n-pentane as the eluent.
Data for 8: a clear colorless liquid, b.p. 53–55 °C/43 mm Hg. 1H
NMR (CDCl3): d 0.21 (d, 3H, J = 3.30 Hz, MeSi), 0.69 (m, 1H, SiCHAC),
0.92 (m, 1H, SiCHBC), 1.69 (dd, 1H, JAB = 14.43, J = 3.91 Hz, SiCHAS),
1.88 (d, 1H, SiCHBS), 2.06 (m, 2H, CCH2C), 2.48 (m, 2H, CCH2S), 4.03
(m, 1H, SiH). 13C NMR (CDCl3): d À5.59 (MeSi), 11.35 (SiCH2C),
11.97 (SiCH2S), 27.17 (CCH2C), 32.21 (CCH2S). 29Si NMR (CDCl3): d
À23.67. Anal. Calc. for C5H12SiS: C, 45.39; H, 9.15; Si, 21.23. Found:
C, 45.17; H, 9.09; Si, 21.14%.
Thioacetate (5) was obtained from pure allyldimethylphenylsi-
lane previously in a similar manner [17].
3.2.4. 3-Methyl-3-phenyl-3-sila-1-thiacyclohexane (6)
A solution of 4 (1.77 g, 6.20 mmol) in methanol (2 mL) was
added to a solution of sodium methoxide (5 mL) prepared from so-
dium (0.14 g, 6.20 g-a). After stirring at room temperature for 3 h,
the reaction mixture was diluted with hexane (10 mL) and
quenched with an aqueous ammonium chloride solution and
water. The aqueous layer was extracted with hexane (2 Â 10 mL),
the combined organic layer was dried (MgSO4), filtered and con-
centrated under reduced pressure. The crude product was purified
by column chromatography (silica gel, hexane/ether, 9:1) to afford
cycle (6) as a colorless oil (0.67 g, 74% yield).
3.2.7. 3-Fluoro-3-methyl-3-sila-1-thiacyclohexane (9)
.
BF3 2CH3COOH (0.5 mL, 3.5 mmol) was added to a stirred solu-
tion of 6 (1.46 g, 7.0 mmol) in CH2Cl2 (5 mL) at room temperature.
The reaction mixture was heated under reflux for 6 h, cooled to
room temperature, and aqueous saturated solution of Na2CO3
(3 mL) was added dropwise until the solution was neutral pH.
The mixture was extracted with CH2Cl2, the combined organic ex-
tracts were dried (MgSO4), filtered and the solvent was removed by
distillation at atmospheric pressure to give 9 (1.34 g, 75% purity, by
1H NMR data). Compound 9 was obtained in 35% yield (0.36 g) by
vacuum distillation.
Data for 6: Rf = 0.70 (hexane/ether, 9:1). 1H NMR (CDCl3): d 0.46
(s, 3H, MeSi), 0.98 (m, 2H, SiCH2C), 1.82 (d, 1H, JAB = 14.8 Hz, Si-
CHAS), 2.11 (d, 1H, SiCHBS), 2.07 (m, 1H, CCHAC), 2.24 (m, 1H,

666
S.V. Kirpichenko, A.I. Albanov / Journal of Organometallic Chemistry 695 (2010) 663–666
Data for 9: a colorless liquid, b.p. 73 °C/26 mm Hg. 1H NMR
(CDCl3): 0.41 (d, 3H, JH–F = 6.9 Hz, MeSi), 0.81 (ddd, 1H,
(b) M.G. Voronkov, S.V. Kirpichenko, E.N. Suslova, L.L. Tolstikova, Zh. Obshch.
Khim. 60 (1990) 2630–2632. J. Gen. Chem. USSR (Engl. Transl.) 60 (1990)
2358–2359.
d
JAB = 14.85, J = 10.50, J = 4.61 Hz, SiCHAC), 0.88 (m, 1H, SiCHBC),
1.72 (d, 1H, JAB = 14.8 Hz, SiCHAS), 1.96 (d, 1H, SiCHBS) 2.00 (m,
1H, CCHAC), 2.27 (m, 1H, CCHBC), 2.43 (m, 2H, CCH2S). 13C NMR
(CDCl3): d À3.93 (d, JC–F = 14.86 Hz, MeSi), 14.07 (d, JC–F = 12.2 Hz,
SiCH2C), 14.54 (d, JC–F = 14.78 Hz, SiCH2S), 28.79 (d, CCH2C, JC–
F = 2.15 Hz), 32.15 (CCH2S). 19F NMR (CDCl3): d À159.45 (d). 29Si
NMR (CDCl3): d À13.35 (d, JSi–F 292.6 Hz). Anal. Calc. for C5H11SiFS:
H, 7.38; Si, 18.69. Found: H, 7.29; Si, 18.12%.
[4] E.N. Suslova, A.I. Albanov, B.A. Shainyan, J. Organomet. Chem. 694 (2009) 420–
426.
[5] K.E. Yelm, Tetrahedron Lett. 40 (1999) 1101–1102.
[6] S.V. Kirpichenko, unpublished results.
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(2007) 10035–10044;
(b) L. Nielsen, T. Skrydstrup, J. Am. Chem. Soc. 130 (2008) 13145–13151.
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Acknowledgment
(b) J.O. Daiss, K.A. Barth, C. Burschka, P. Hey, R. Ilg, K. Klemm, I. Richter, S.A.
Wagner, R. Tacke, Organometallics 23 (2004) 5193–5197;
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This work was supported by the Russian Foundation for Basic
Research and Deutsche Forschungsgemeinschaft (Grant RFBR-
DFG No. 08-03-91954).
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