Reaction of tetra(phenylethynyl)tin with aromatic aldehydes: A new one-pot method for the synthesis of α-acetylene ketones

Article abstract of DOI:10.1134/S1070363217070295

The reaction of tetra(phenylethynyl)tin with aromatic aldehydes in the presence of ZnCl₂ afforded α-acetylene ketones in a yield of 77–98%.

Full text of DOI:10.1134/S1070363217070295

ISSN 1070-3632, Russian Journal of General Chemistry, 2017, Vol. 87, No. 7, pp. 1627–1630. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © A.S. Levashov, D.S. Buryi, V.V. Konshin, V.V. Dotsenko, N.A. Aksenov, I.V. Aksenova, 2017, published in Zhurnal Obshchei Khimii,
2017, Vol. 87, No. 7, pp. 1200–1203.
LETTERS
TO THE EDITOR
Reaction of Tetra(phenylethynyl)tin with Aromatic Aldehydes:
A New One-Pot Method for The Synthesis
of α-Acetylene Ketones
A. S. Levashova*, D. S. Buryia, V. V. Konshina,
V. V. Dotsenkoa,b, N. A. Aksenovb,c, and I. V. Aksenovab
a Kuban State University, ul. Stavropol’skaya 149, Krasnodar, 350040 Russia
*e-mail: aslevashov@mail.ru
b North-Caucasus Federal University, Stavropol, Russia
c Russian People’s Friendship University, Moscow, Russia
Received March 16, 2017
Abstract―The reaction of tetra(phenylethynyl)tin with aromatic aldehydes in the presence of ZnCl2 afforded
α-acetylene ketones in a yield of 77–98%.
Keywords: α-acetylene ketones, tin acetylenides, Lewis acid
DOI: 10.1134/S1070363217070295
α-Acetylene ketones are sufficiently reactive com-
pounds widely used as substrates in the construction of
various carbo- and heterocyclic compounds, like
polyfunctional pyrroles [1], chromones [2, 3],
indenones [4], quinolones [5], benzodiazepines [6],
spirocycles [7], etc.
reactions with organometallic [17] or organoboron
compounds [18].
Recently we showed the possibility of using tetra-
alkynylstannanes (RC≡C)4Sn in the Stille cross-
coupling reaction with aryl halides [19]. It should be
noted that all four alkynyl moieties are involved into
this process, i. e., the reaction has a high E-factor, and
produced relatively low toxic inorganic tin(IV) halides
as a by-product.
One of the general methods of the preparation of
α-acetylene ketones involves the reaction of metal
acetylides with aldehydes, followed by oxidation of
propargyl alcohols [2, 5, 8–11].
In continuation of our research, here we studied the
reactivity of tin tetraalkynides with respect to aromatic
aldehydes. Thus, it was found that the reaction of tetra-
(phenylethynyl)tin 1 with aromatic aldehydes 2a–2c
occurred only in the presence of ZnCl2 at 60°C.
Contrary to the expectations, α-acetylene ketones 4a–
4c were obtained as the main products instead of pro-
pargyl alcohols 3.
Trialkylstannylacetylenes are inert with respect to
many functional groups, therefore they are actively
used as alkynylating reagents in the construction of
complex organic structures, including cross-coupling
reactions [12, 13]. We have previously developed effec-
tive methods for the preparation of tin tetraacetylides
from 1-alkynes and tin tetrachloride [14, 15] or tin
tetra(N,N-dialkylcarbamates) [16]. It was expectable
that the resulting tetraalkynylstannanes (RC≡C)4Sn
will have several advantages over trialkylstannyl-
acetylenes Alk3Sn–C≡C–R, due to atom-efficiency and
lesser toxicity. To date, the properties of tin tetra-
acetylides have been studied insufficiently and their
application in organic synthesis is limited to several
The reaction mechanism presumably includes the
Oppenauer oxidation stage similar to the oxidative
addition of alkynes to aldehydes in the presence of
indium bromide [20]. The tin alkoxides formed in the
first stage are rapidly oxidized by Oppenauer reaction
with the second aldehyde molecule to form ketone 4
and the corresponding alcohol.
1627

1628
LEVASHOV et al.
Scheme 1.
OH
Ar
O
Ph
Ph
Ph
Ph
Ph
Ph
ZnCl2
3
Sn
Ar
O
PhMe
1
2a_2c
Ar
4a_4c
O
(a),
Ar
(b),
(c).
=
O
F
Toluene was the best solvent for the process, while
in ether solvents only trace amounts of the reaction
product 4a were detected (see the table). Target
α-acetylene ketones 4a–4c were readily isolated by
column chromatography eluting with toluene. The
structure of the obtained compounds was confirmed by
1H, 13C NMR, IR spectroscopy, and chromatography-
mass spectrometry. The structure of the previously
unknown 1- (2,3-dihydro-1,4-benzodioxin-6-yl)-3-phenyl-
prop-2-yn-1-one 4c was additionally confirmed by
X-ray diffraction (XRD) analysis (see the figure and
Scheme 1).
1,3-Diphenylprop-2-yn-1-one (4a). A mixture of
anhydrous ZnCl2 (10.4 mg, 0.076 mmol), toluene
(0.8 mL), tetra(phenylethynyl)tin (100 mg, 0.191 mmol),
and freshly distilled benzaldehyde (155 μL, 1.53 mmol)
was stirred at 60°C for 5 h. The reaction mixture was
treated with 1 M HCl solution. The reaction product
was extracted with chloroform and purified by column
chromatography (eluent toluene). Yield 154 mg (97%),
pale yellow liquid. IR spectrum, ν, cm–1: 3099, 3082,
3059, 3034, 2199 (С≡С), 1642 (С=О), 1597, 1582. 1Н
NMR spectrum (CDCl3), δ, ppm: 7.39−7.53 m (5H,
ArH), 7.60−7.69 m (3H, ArH), 8.22 d (2H, ArH, J =
7.3 Hz). 13C NMR spectrum (CDCl3), δС, ppm: 86.8,
93.1, 120.1, 128.6, 128.7, 129.5, 130.8, 133.0, 134.1,
136.8, 177.9. Mass spectrum (EI, 70 eV), m/z (Irel, %):
206 (52) [М]+, 178 (88), 152 (11), 129 (100), 101 (14),
89 (11), 77 (26), 76 (21), 75 (33), 51 (35).
In summary, tetra(phenylethynyl)tin reacted with
aromatic aldehydes in the presence of zinc chloride to
form acetylene ketones. The suggested reaction me-
chanism involves the Oppenauer oxidation of inter-
mediates. The advantage of the new method is a high
atom-economy, availability of reagents, one-stage
process, and no toxic waste.
3-Phenyl-1-(4-fluorophenyl)prop-2-yn-1-one (4b)
was prepared similarly from tetra(phenylethynyl)tin
(100 mg, 0.191 mmol) and 4-fluorobenzaldehyde
(164 μL, 1.53 mmol). The reaction product was
isolated by column chromatography, eluent toluene.
Yield 168 mg (98%), yellow liquid. IR spectrum, ν, cm–1:
Tetra(phenylethynyl)tin was prepared according to
the procedure [14]. Aromatic aldehydes were pur-
chased from Aldrich.
Effect of the reaction conditions on the yield of compound 4
Run no.
Aldehyde
1:2
1:4
1:4
1:4
1:8
1:8
1:8
Solvent
1,4-Dioxane
Toluene
Time, h
Yield, %a
1
2a
2a
2a
2a
2б
2в
24
5
4
50
0
2
3b
4
5
Toluene
Toluene
5
97
98
77
Toluene
5
1
Toluene
6
5
a Yield was calculated relative to tetra(phenylethynyl)tin. b In the absence of ZnCl2.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 87 No. 7 2017

REACTION OF TETRA(PHENYLETHYNYL)TIN WITH AROMATIC ALDEHYDES
1629
Crystal structure of 1-(2,3-dihydro-1,4-benzodioxin-6-yl)-3-phenylprop-2-yn-1-one 4c.
3074, 3065 (С–H), 2199 (С≡С), 1643 (С=О), 1608,
1595. Н NMR spectrum (CDCl3), δ, ppm: 7.02–7.15
Crystals of compound 4c were obtained by
recrystallization from hexane–chloroform mixture (8 : 2).
Monoclinic crystals, C17H12O3, M 264.27, space group
P21/c (no. 14); the unit cell parameters at 100 K are as
follows: a 12.6774(2), b 11.4801(2), c 18.9403(3) Å, β
108.896(2)°, V 2607.97(8) Å3, Z 8, dcalc 1.346 g/cm3,
μ(CuKα) 0.751 mm–1. The unit cell parameters and
intensity of 49562 reflections (7.37° ≤ 2θ ≤ 148.63°)
(5431 independent reflections, Rint 0.0658) were
measured on an Agilent Super Nova Dual (Cu at zero)
Atlas S2 diffractometer. The final divergence factors
areas follows: R1 0.0746 for 5431 independent
reflections with I > 2σ(I) and wR2 0.2357 for all
reflections. Structure was solved and refined by the
least squares method using Olex2 program package
[21] and ShelXT and ShelXL software [22].
Crystallographic data including atomic coordinate
tables, temperature factors, tables of bond lengths and
bond angles were deposited at the Cambridge
1
m (2H), 7.29–7.42 m (3H), 7.53–7.61 m (2H), 8.11–
8.20 m (2H). 13C NMR spectrum (CDCl3), δС, ppm:
86.7, 93.5, 116.0 d (J = 21.9 Hz), 120.0, 128.7, 131.0,
132.3 d (J = 9.7 Hz), 133.1, 133.5 d (J = 3.2 Hz),
166.4 d (J = 256.9 Hz), 176.4.
1-(2,3-Dihydro-1,4-benzodioxin-6-yl)-3-phenyl-n-
prop-2-yn-1-one (4c) was prepared similarly from
tetra(phenylethynyl)tin (64.4 mg, 0.123 mmol) and 2,3-
dihydro-1,4-benzodioxin-6-carbaldehyde (161.9 mg,
0.986 mmol). The reaction product was isolated by
column chromatography, eluent toluene. Yield 100 mg
(77%), pale yellow crystals, mp 98.5–99.7°C (hexane–
chloroform). IR spectrum (KBr), ν, cm–1: 3065 (Сsp2-
H), 2986, 2938, 2922, 2891, 2876 (Сsp3-H), 2203
1
(С≡С), 1626 (С=О), 1601, 1584. Н NMR spectrum
(CDCl3), δ, ppm: 4.28–4.30 m (2Н, OCH2), 4.32–4.34
m (2Н, OCH2), 6.95 d (1H, ArH, J = 8.2 Hz), 7.38–
7.48 m (3H, ArH), 7.64–7.66 m (2H, ArH), 7.74–7.77
m (2H, ArH). 13C NMR spectrum (CDCl3), δС, ppm:
64.2, 64.9, 87.0, 92.4, 111.5, 119.0, 120.4, 124.0, 128.7,
130.7, 131.1, 133.1, 143.5, 149.2, 176.6. Mass spectrum
(EI, 70 eV), m/z (Irel, %): 264 (100) [М]+, 236 (53), 180
(49), 152 (50), 129 (65), 126 (15), 101 (11), 75 (18),
51 (23).
1
Structural Data Centre (CCDC 1535382). H and 13C
NMR spectra were recorded on a JEOL ECA400
instrument in a CDCl3 solution using tetramethylsilane
as reference. IR spectra were registered on an Infralum
FT-02 (Lumex) spectrometer. The reaction progress
was monitored by chromatography-mass spectrometry
using a Shimadzu GC-2010 instrument equipped with
a Shimadzu QP-2010 mass-selective detector (Supelko
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LEVASHOV et al.
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The studies were carried out with the use of
equipment of the Scientific Educational Center
“Diagnostics of the Structure and Properties of
Nanomaterials.” This work was financially supported
by the Ministry of Education and Science of Russia
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