Insertion of an Isolable Dialkylstannylene into C-Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

Article abstract of DOI:10.1021/acs.organomet.7b00549

The reactions of isolable dialkylstannylene 1 with 1-adamantanoyl, 2,2-dimethylpropanoyl, benzoyl, and substituted benzoyl chlorides afford the corresponding acyl(chloro)stannanes in good yields. Similar reactions with more reactive acetyl and propanoyl c

Full text of DOI:10.1021/acs.organomet.7b00549

Article
pubs.acs.org/Organometallics
Insertion of an Isolable Dialkylstannylene into C−Cl Bonds of Acyl
Chlorides Giving Acyl(chloro)stannanes
Qiong Lu, Chenting Yan, Xu-Qiong Xiao, Zhifang Li,* Ningka Wei, Guoqiao Lai,* and Mitsuo Kira*
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University,
Hangzhou, 311121, Zhejiang, People’s Republic of China
S
* Supporting Information
ABSTRACT: The reactions of isolable dialkylstannylene 1
with 1-adamantanoyl, 2,2-dimethylpropanoyl, benzoyl, and
substituted benzoyl chlorides afford the corresponding acyl-
(chloro)stannanes in good yields. Similar reactions with more
reactive acetyl and propanoyl chlorides do not give the
corresponding insertion products but the corresponding
dichlorostannane by the overreaction. The benzoyl(chloro)-
stannane reacts with acetyl chloride to afford the correspond-
ing 1,2-dione and the dichlorostannane quantitatively. Acyl-
(chloro)stannanes obtained were fully characterized by multinuclear NMR spectroscopy, high-resolution mass spectrometry, and
by single-crystal X-ray diffraction studies.
its molecular structure was determined by X-ray diffraction
technique.12
INTRODUCTION
■
Acylsilanes and their heavier congeners, acylgermanes and
acylstannanes, have been known as an electronically unique
class of group-14 element compounds1 with remarkably red-
shifted n → π* transition bands due to enhanced σ−n
conjugation.2 Since the first synthesis of a benzoylsilane by
Brook,3 a number of methods for the synthesis of various
acylsilanes have been devised4 and they have been applied for
the organic synthesis5,6 and for the synthesis of structurally
interesting silicon compounds; acyltris(trimethylsilyl)silanes
were utilized for the synthesis of the first stable silicon−carbon
doubly bonded compounds (silenes).7 More recently, an
isolable silenyllithium was synthesized using an acyl(halo)-
silane.8 On the contrary, less attention has been focused on the
corresponding acylstannanes,9 despite their great potential in
synthetic organic chemistry. Acylstannanes have often been
synthesized using the reactions of acyl chlorides (or carboxylic
acid esters and thioesters) with stannyllithiums9a,d and those
with hexamethyldistannane in the presence of palladium
catalysts9e (eqs 1 and 2), and using some other specific
reactions such as photolysis of stannylfuranes.9f A number of
applications of the acylstannanes for the organic synthesis have
been reported.10
We have recently reported a similar insertion of an isolable
dialkylsilylene as a conventional synthetic method for the
corresponding acyl(chloro)silanes D (Chart 1).13 During the
course of our studies of the reactions of isolable dialkyl-
stannylene 1 (Chart 1) with various functional groups,14 we
have found that the stannylene inserts exclusively into the C−
Cl bonds of acyl chlorides, providing a number of acyl(chloro)-
stannanes that are difficult to synthesize via conventional
methods. They are expected to be more reactive than the
corresponding acylsilanes and to serve as better synthetic
reagents.
RESULTS AND DISCUSSION
■
When dialkylstannylene 1 was treated with an excess amount of
benzoyl and 4-substituted benzoyl chlorides 2a−2c in hexane at
room temperature, the corresponding benzoyl(chloro)-
stannanes 3a−3c were obtained in good yields, indicating
that the C−Cl bond is much more reactive than the carbonyl
group (eq 3). No significant difference was observed in the
reactivity among benzoyl chlorides 2a−2c. The results are
summarized in Table 1.
Insertion of isolable diamino- and dialkylstannylenes A and B
(Chart 1) into acyl−Cl bonds of acyl chlorides, giving
acyl(chloro)stannanes, has first reported by Lappert and co-
workers in 1987.11 Recently, a thermally less stable acyl-
(chloro)stannane was isolated through the reaction of a C,N-
chelated stannylene (C) (Chart 1) with benzoyl chloride, and
Received: July 21, 2017
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.7b00549
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Chart 1. Structural Formulae of Lappert’s Stannylenes (A and B), Double C,N-Chelated Stannylene (C), Benzoyl(chloro)silanes
(D), and 1
Table 1. Yields and Spectral Data of Acylstannanes
Similarly, compounds 3b and 3c were crystallized in space
groups P21/c and P−1, and their molecular structures are shown
in Figures 2 and 3. In contrast to 3a having two crystallo-
a
b
c
d
entry compound yield (%) δ (13C)
δ (119Sn)
ν (CO) (cm−1
)
1
2
3
4
5
3a
3b
3c
3d
3e
92
82
76
84
78
230.4
229.2
231.1
241.8
243.5
71.9
72.2
72.5
61.5
60.6
1639
1628
1634
1652
1655
a
b
Isolated yields. Spectra recorded in CDCl3. Chemcial shifts (ppm)
c
d
are based on external Me4Si. Based on external Me4Sn. Determined
by ATR-FTIR.
Molecular structures of compounds 3a−3c were determined
by X-ray single-crystal diffraction analysis. Yellow single crystals
of 3a−3c suitable for X-ray crystallography were obtained by
slowly evaporating the solvent from their hexane solutions. The
ORTEP drawing of compound 3a is depicted in Figure 1
together with pertinent structural parameters. Compound 3a
crystallizes in the P21/c space group. The unit cell contains two
independent molecules in an asymmetric unit with different
torsion angles of C(1)Sn(1)C(17)O(1) and its equivalent,
C(24)Sn(6)C(40)O(2), (130.8° and 134.8°, respectively).
Because the other structural parameters of the two molecules
are very similar, we will discuss the feature on the molecule
with Sn(1). The sum of bond angles around C(17) is 360°,
being in accord with the sp2 character of the carbonyl carbon
atom. The distance of the Sn(1)−Cl(1) (2.394(2) Å) bond is
longer than that of chloro(triphenyl)tin (2.35 Å),15 but shorter
than those of trialkyl derivatives such as Cy3SnCl (2.4558 Å, Cy
= cyclohexyl)16 and Me3SnCl (2.43 Å).17 The C(17)O(1)
bond distance of 1.192(7) Å is significantly shorter than those
of the corresponding acyl(chloro)silanes (D, 1.217−1.223 Å).13
Figure 2. ORTEP drawing of compound 3b. (Hydrogen atoms are
omitted for clarity. Thermal ellipsoids are shown at the 30%
probability level.) Selected bond lengths (Å) and angles (deg):
Sn(1)−C(4) 2.174(3), Sn(1)−C(1) 2.186(3), Sn(1)−C(17)
2.235(3), Sn(1)−Cl(1) 2.3841(8), C(18)−C(17) 1.485(4), O(1)−
C(17) 1.203(4), C(4)−Sn(1)−C(1) 93.37(10), C(4)−Sn(1)−C(17)
115.78(11), C(1)−Sn(1)−C(17) 129.95(11), C(4)−Sn(1)−Cl(1)
110.05(8), C(1)−Sn(1)−Cl(1) 110.95(8), C(17)−Sn(1)−Cl(1)
96.67(8), O(1)−C(17)−C(18) 122.8(3), O(1)−C(17)−Sn(1)
115.2(2), C(18)−C(17)−Sn(1) 122.0(2).
graphically independent molecules in an asymmetric unit, 3b or
3c has one molecule in a unit cell. Their structural parameters
are similar to those of 3a.
Figure 1. ORTEP drawing of compound 3a. (Hydrogen atoms are omitted for clarity. Thermal ellipsoids are shown at the 30% probability level.)
Selected bond lengths (Å) and angles (deg): Sn(1)−C(4) 2.165(5), Sn(1)−C(1) 2.183(6), Sn(1)−C(17) 2.219(6), Sn(1)−Cl(1) 2.394(2), O(1)−
C(17) 1.192(7), C(17)−C(18) 1.457(9), C(4)−Sn(1)−C(1) 94.4(2), C(4)−Sn(1)−C(17) 119.5(2), C(1)−Sn(1)−C(17) 126.5(2), C(4)−
Sn(1)−Cl(1) 110.94(16), C(1)−Sn(1)−Cl(1) 111.10(17), C(17)−Sn(1)−Cl(1) 94.83(18), O(1)−C(17)−C(18) 120.3(6), O(1)−C(17)−Sn(1)
116.7(5), C(18)−C(17)−Sn(1) 123.0(5), C(19)−C(18)−C(17) 122.7(8).
B
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Scheme 1. Reactions of Alkanoyl Chlorides 2d−2g with
Dialkylstannane 1
umpolung of a nucleophilic acyl chloride into an electrophilic
acylstannane.8
Figure 3. ORTEP drawing of compound 3c. (Hydrogen atoms are
omitted for clarity. Thermal ellipsoids are shown at the 30%
probability level.) Selected bond lengths (Å) and angles (deg):
Sn(1)−C(4) 2.168(3), Sn(1)−C(1) 2.184(3), Sn(1)−C(17)
2.226(3), Sn(1)−Cl(1) 2.3891(9), C(17)−O(1) 1.195(4), C(17)−
C(18) 1.497(4), C(4)−Sn(1)−C(1) 93.49(10), C(4)−Sn(1)−C(17)
116.22(10), C(1)−Sn(1)−C(17) 132.25(11), C(4)−Sn(1)−Cl(1)
111.88(8), C(1)−Sn(1)−Cl(1) 111.30(8), C(17)−Sn(1)−Cl(1)
92.12(9), O(1)−C(17)−C(18) 121.6(3), O(1)−C(17)−Sn(1)
115.3(2), C(18)−C(17)−Sn(1) 123.0(2), C(23)−C(18)−C(17)
121.2(3), C(19)−C(18)−C(17) 119.5(3).
Scheme 2. Pathway of the Formation of 4
Due to the umpolung, an acyl(chloro)stannane may react
with HCl and another acyl chloride to give the corresponding
aldehyde and 1,2-dione, respectively. Actually, benzoyl(chloro)-
stannane 3a reacts with HCl in hexane at room temperature to
afford benzaldehyde together with 4 in good yields (eq 4).
The NMR spectra of 3a−3c in CDCl3 are consistent with
1
their structures in the solid states. Typically, the H NMR
spectrum reveals two singlet signals for the four trimethylsilyl
groups in the region of 0.1−0.3 ppm [0.16, 0.28 (3a); 0.17,
0.28 (3b); 0.17, 0.29 (3c)], indicating that there are two types
of trimethylsilyl groups because of their Cs symmetry of 3. In
accord with the observation, two singlet 13C and 29Si NMR
signals were observed for the trimethylsilyl groups in 3a−3c, at
3.1.and 3.6 ppm in the 13C NMR, and at ca. 5.7 and 3.2 ppm in
the 29Si NMR. The signals at 230.4 (3a), 229.2 (3b), and 231.1
(3c) ppm in 13C NMR spectra are ascribed to the carbonyl
carbon signals, which are at higher field than those of the
typical acylstannanes (δ ca. 240 ppm)9d but at lower field than
those of the corresponding acyl(chloro)silanes (δ 224.5−225.3
ppm).13 The 119Sn NMR resonances due to the ring tin atom of
3a−3c appear at the similar chemical shifts of 72 ppm. In the IR
spectra of 3, a strong absorption was observed at around 1630
or 1650 cm−1, which can be attributed to the CO stretching
mode. The frequencies are lower than those for usual ketones
such as PhCOtBu (ν (CO) = 1675 cm−1)18a but a little higher
than those for related acylmetals like PhCOSiMe3 (ν (CO) =
1618 cm−1),18b PhCOGeEt3 (ν (CO) = 1629 cm−1),4a and
PhCOSnMe3 (ν (CO) = 1620 cm−1).9d
Similarly to aroyl chlorides, 1-adamantanoyl 2d and 2,2-
dimethylpropanoyl chlorides 2e also readily furnished the
corresponding 1:1 adducts 3d and 3e in good yields (Scheme
1). Products 3d and 3e were fully characterized by NMR,
DODI-TOF, IR, and EA. In contrast to 2a−2e, propanoyl
chloride 2f and acetyl chloride 2g reacted with 1 under similar
reaction conditions but did not give the corresponding
acylstannanes. Thus, the reactions of 1 with 2 mol of 2f and
2g afforded the corresponding dichlorostannane 4 in 78% and
76% yields, respectively. The formation of the corresponding
1,2-diones, hexane-3,4-dione, and butane-1,2-dione, in 30% and
40%, was shown by GC−MS analysis of the reaction mixture.
In the reactions of 1 with more reactive acyl chlorides, 2f and
2g, 3f and 3g once formed would be decomposed by another
acyl chloride molecule to give 4 (Scheme 2), indicating
The reaction of 3a with acetyl chloride gave 1-phenyl-
propane-1,2-dione in a high yield, while 3a did not react with
less reactive benzoyl chloride in the similar conditions (Scheme
3). The reactions of acylstannanes with acyl chlorides have
Scheme 3. Reaction of 3a with Acetyl Chloride or Benzoyl
Chloride
been reported to occur in the presence of palladium catalysts,
giving the corresponding 1,2-diones.10a The reaction would
occur concertedly through the nucleophilic attack of the
anionic chlorine atom of acetyl chloride to the tin atom of 3a
leaving benzoyl group, which would be captured simultaneously
by the cationic acetyl carbon to form the 1,2-dione; it is
interesting to note that the benzoyl group may be regarded as
an equivalent to a chlorine atom similarly to ethoxyethyl
group.19
In conclusion, the reactions of isolable dialkylstannylene 1
with acyl chlorides (aroyl, 1-adamantanoyl, and 2,2-dimethyl-
propanoyl chlorides) afforded acylstannanes 3a−3e exclusively.
Propanoyl and acetyl chlorides react with 1 to give the
corresponding dichlorostannane 4 by overreaction. Aroyl-
(chloro)stannane 3a further reacted with acetyl chloride to be
transformed into the corresponding 1,2-dione and 4
quantitatively.
C
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Then, the reaction mixtures were checked by GC−MS directly, and
found the formation of biacetyl (30%) or hexane-3,4-dione (40%) in
addition to dichlorostannane 4, which was obtained by recrystallization
from a 1:1 mixture of hexane and EtOH as a colorless solid in 78% or
76%. 4: mp: 190 °C (lit.14b187−188 °C); 1H NMR (400 MHz,
CDCl3) δ 2.27 (s, 4H), 0.25 (s, 36H); 13C NMR (101 MHz, CDCl3) δ
31.5, 24.9, 3.3; 29Si NMR (79 MHz) δ 4.81; 119Sn NMR (187
MHzCDCl3) δ 182.6.
Reaction of 3a with Acetyl Chloride. A hexane solution of acetyl
chloride (78.5 mg, 1 mmol) was added dropwise into 3a (121 mg, 0.2
mmol) in hexane (210 mL) in a Schlenk tube at room temperature,
and then the reaction mixture was stirred for 12 h. The solvent was
removed under vacuum, and the products were isolated as pure
substances from the resulting residue by flash chromatography.
Dichlorostannane 4 and phenylpropane-1,2-dione were isolated in
95% and 89%, respectively. 1-Phenylpropane-1,2-dione: 1H NMR
(400 MHz, CDCl3) δ 7.93−7.95 (d, J = 8.0 Hz, 2H), 7.42−7.57 (m,
3H), 2.45 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 200.4, 191.3,
134.4, 131,8, 130.2, 128.7, 26.2.
Reaction of 3a with HCl. In a Schlenk tube (25 mL) was placed
3a (121 mg, 0.2 mmol) and hexane (10 mL), and then HCl gas was
bubbled into the tube for 30 min. The mixture was stirred at room
temperature for an additional 2 h. After separation using column
chromatography, compound 4 and benzaldehyde were obtained in
99% and 75%, respectively; the latter yield was determined by GC−
MS.
X-ray Structure Determination. Single crystals of 3a, 3b, and 3c
suitable for X-ray analysis were obtained by the recrystallization from
hexane. The X-ray diffraction data were collected on a Bruker Smart
Apex CCD diffractometer with graphite monochromated Mo−Kα
radiation (λ = 0.71073 Å) using the ω-2θ scan mode. The structures
were solved by direct methods and refined on F2 by full-matrix least-
squares methods using SHELX-2000.20 Crystal and refinement data
for 3a−3c are described in the SI. The supplementary crystallographic
data for 3a, 3b, and 3c are deposited with the CCDC; the Nos. are
1534786, 1534785, and 1534784, respectively.
EXPERIMENTAL SECTION
■
Manipulation of air-sensitive compounds was performed under a
controlled dry argon atmosphere using standard Schlenk techniques.
Hexane was distilled from sodium−benzophenone. All the other
reagents were obtained from commercial suppliers and used without
further purification. Dialkylstannylene 1 was prepared according to
literature procedures.14a Stannlylene 1 and other air-sensitive materials
were handled in an MBraun glovebox. 1H (400 MHz), 13C (101
MHz), 29Si (79 MHz), and 119Sn (187 MHz) NMR spectra were
recorded on a BRUKER AV-400 MHz instrument using Me4Si (1H,
13C, and 29Si) and Me4Sn (119Sn) as external standards. Mass spectra
were measured with a Bruker Daltonics Autoflex IITMMALDI-TOF
spectrometer. IR spectra were recorded by attenuated total reflection
with a diamond single reflection plate using a Bruker Vertex 70
instrument. Elemental analyses were performed on a VARIO EL-III
instrument.
The full 1H, 13C, 29Si, and 119Sn NMR spectra of all new compounds
(3a−3e) are provided in the Supporting Information (SI).
Synthesis of 3a−3e. A hexane solution of acyl chloride (0.96
mmol) was added to a hexane solution of dialkylstannylene 1 (0.3 g,
0.64 mmol) at room temperature. The color of the solution changed
from red to yellow quickly. The reaction mixture was allowed to stir
for 2−3 h, and then the solvent was removed under vacuum. The
resulting residue was purified by a preparative silica-gel column to give
3 as a yellow solid.
1
3a, Yield: (0.36g, 92%); mp: 99.0−99.5 °C; H NMR (400 MHz,
CDCl3) δ 7.98−8.00 (m, 2H,), 7.56−7.63 (m, 3H), 2.35−2.16 (m,
4H), 0.28 (s, 18H), 0.16 (s, 18H); 13C NMR (101 MHz, CDCl3) δ
230.3, 138.5, 134.3, 130.3, 129.0, 33.8, 21.5, 3.6, 3.1; 29Si NMR (79
MHz) δ 5.71, 3.37; 119Sn NMR (187 MHz, CDCl3) δ 71.9; MALDI-
TOF-MS m/z Calcd for C23H45ClOSi4Sn: 604; Found: 604; Anal.
Calcd for C23H45ClOSi4Sn: C, 45.73; H, 7.51; O, 2.65. Found: C,
45.69; H, 7.53; O, 2.62.
1
3b, Yield: (0.33g, 82.5%); mp: 142.8−143.7 °C; H NMR (400
MHz, CDCl3) δ 7.87−7.89 (d, J = 8 Hz, 2H), 7.36−7.38 (d, J = 8 Hz,
2H), 2.45 (s, 3H), 2.15−2.32 (m, 4H), 0.28 (s, 18H), 0.17 (s, 18H);
13C NMR (101 MHz, CDCl3) δ 229.2, 145.5, 136.1, 130.5, 129.8, 33.8,
21.8, 21.3, 3.6, 3.1; 29Si NMR (79 MHz) δ 5.68, 3.35; 119Sn NMR
(187 MHz, CDCl3) δ 72.2; MALDI-TOF-MS m/z Calcd for
C24H47ClOSi4Sn: 618; Found:618; Anal. Calcd for C24H47ClOSi4Sn:
C, 46.63; H, 7.66; O, 2.59. Found: C, 46.57; H, 7.58; O, 2.66.
3c, Yield: (0.11 g, 76%); mp: 126.2−126.6 °C; 1H NMR (400 MHz,
CDCl3) δ 8.11−8.13 (d, J = 8 Hz, 2H), 7.84−7.86 (d, J = 8 Hz, 2H),
2.17−2.36 (m, 4H), 0.29 (s, 18H), 0.17 (s, 18H); 13C NMR (101
MHz, CDCl3) δ 231.0, 140.7, 135.0, 130.1, 126.1, 124.7, 33.7, 22.0,
3.6, 3.1; 29Si NMR (79 MHz) δ 5.82, 3.46; 119Sn NMR (187 MHz,
CDCl3) δ 72.5; MALDI-TOF-MS m/z Calcd for C24H44ClF3OSi4Sn:
672; Found:672; Anal. Calcd for C24H44ClF3OSi4Sn: C, 42.89; H,
6.60; O, 2.38. Found: C, 42.97; H, 6.58; O, 2.33.
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.7b00549.
1H, 13C, 29Si, and 119Sn NMR spectra of 3a−3e and 4
and X-ray crystallography of compounds 3a, 3b, and 3c
(PDF)
Accession Codes
3d, Yield: (0.24g, 84%); mp: 104.2−105.0 °C; 1H NMR (400 MHz,
CDCl3) δ 2.28−2.18 (m, 3H), 2.13 (s, 4H), 2.05 (s, 6H), 1.76 (s, 6H),
0.22 (s, 18H), 0.18 (s, 18H); 13C NMR (101 MHz, CDCl3) δ 242.1,
54.9, 37.8, 36.5, 33.7, 28.2, 22.8, 3.8, 3.4; 29Si NMR (79 MHz) δ 5.69,
3.11; 119Sn NMR (187 MHz, CDCl3) δ 61.5; MALDI-TOF-MS m/z
Calcd for C27H55ClOSi4Sn: 662; Found: 662; Anal. Calcd for
C27H55ClOSi4Sn: C, 48.97; H, 8.37; O, 2.42. Found: C, 48.89; H,
8.45; O, 2.35.
CCDC 1534784−1534786 contain the supplementary crystal-
lographic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
3e, Yield: (0.22g, 78%); mp: 151 °C; 1H NMR (400 MHz, CDCl3)
δ 2.29−2.13(m, 4H), 1.34 (s, 9H), 0.22 (s, 18H), 0.18 (s, 18H); 13C
NMR (101 MHz, CDCl3) δ 243.5, 52.5, 33.7, 25.9, 22.6, 3.7, 3.3; 29Si
NMR (79 MHz) δ 5.70, 3.18; 119Sn NMR (187 MHz, CDCl3) δ 60.6;
Anal. Calcd for C21H49ClOSi4Sn: C, 43.18; H, 8.46. Found: C, 43.09;
H, 8.55.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: zhifanglee@hznu.edu.cn (Z.L.).
*E-mail: gqlai@hznu.edu.cn (G.L.).
*E-mail: mkira@m.tohoku.ac.jp (M.K.).
Reaction of Dialkylstannylene 1 with Acetyl Chloride or
Propanoyl Chloride. A hexane solution of HCl-free acetyl chloride
(39.3 mg, 0.5 mmol) or propanoyl chloride (46.25 mg, 0.5 mmol) was
added to a solution of dialkylstannylene 1 (0.1 g, 0.2 mmol) in hexane
at room temperature. The color of the solution changed from red to
colorless quickly. The reaction mixture was allowed to stir for 2 h.
ORCID
Zhifang Li: 0000-0002-9548-2158
Notes
The authors declare no competing financial interest.
D
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Article
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ACKNOWLEDGMENTS
■
This work was supported by the National Natural Science
Foundation of China (Grant No. 21472032) and the Natural
Science Foundation of Zhejiang Province (Grant No.
LY17B010002).
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DOI: 10.1021/acs.organomet.7b00549
Organometallics XXXX, XXX, XXX−XXX