A Simple Synthesis of 1,3-Diphenylpropene

Article abstract of DOI:10.1134/S1070363218020251

A simple approach to the synthesis of 1,3-diphenylpropene isomers was developed based on Fe(acac)₃-catalyzed cross-coupling of (E)- and (Z)-1,3-dichloropropenes with phenylmagnesium bromide.

Full text of DOI:10.1134/S1070363218020251

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 2, pp. 342–344. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © R.N. Shakhmaev, A.Sh. Sunagatullina, A.N. Vasilyeva, V.V. Zorin, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88,
No. 2, pp. 346–348.
LETTERS
TO THE EDITOR
A Simple Synthesis of 1,3-Diphenylpropene
R. N. Shakhmaev*, A. Sh. Sunagatullina, A. N. Vasilyeva, and V. V. Zorin
Ufa State Petroleum Technological University, ul. Kosmonavtov 1, Ufa, 450062 Russia
*e-mail: biochem@rusoil.net
Received October 26, 2017
Abstract—A simple approach to the synthesis of 1,3-diphenylpropene isomers was developed based on
Fe(acac)3-catalyzed cross-coupling of (E)- and (Z)-1,3-dichloropropenes with phenylmagnesium bromide.
Keywords: 1,3-diphenylpropene, cross-coupling, Fe-catalyzed cross-coupling, Fe(acac)3
DOI: 10.1134/S1070363218020251
1,3-Diphenylpropene isomers are used in organic
synthesis as the starting substrates and model
compounds [1–4]. The specific reactivity of 1,3-di-
phenylpropene is due to the presence of methylene
group, being simultaneously in the allyl and benzyl
positions. (E)-1,3-Diphenylpropene is usually obtained
by treating a not easily accessible phenylacetaldehyde
with a KOH alcohol solution [5, 6], while the synthesis
of less thermodynamically stable (Z)-isomer with an
acceptable stereochemical purity is very problematic
[7, 8].
92 : 8) in a 52% yield. The introduction of the most
frequently used ligands like N,N,N,N-tetramethylethyl-
enediamine (TMEDA) [22] or N-methylpyrrolidone
(NMP) [10], the replacement of THF by diethyl ether
and the use of FeCl3 as the catalyst did not sub-
stantially increase the yield of the reaction product.
However, a decrease in the reaction temperature to
–35°C results in an increase in the yield of 1,3-diphenyl-
propene to 80% with the same isomeric composition.
The cross-coupling with (Z)-1,3-dichloropropene
under similar conditions resulted in an isomeric mixture
of 1,3-diphenylpropene (E : Z = 55 : 45) with 72%
yield, while at room temperature the reaction direction
shifted toward the formation of (E)-isomer (E : Z =
76 : 24). (E)- and (Z)-isomers of 1,3-diphenylpropene
and diphenyl formed by homocoupling reaction were
separated by column chromatography (Scheme 1).
We investigated the possibility of obtaining 1,3-
diphenylpropene 2 by Fe(acac)3-catalyzed cross-
coupling of 1,3-dichloropropene 1 with phenylmag-
nesium bromide. It is known that available iron(III)
salts are effective catalysts in cross-coupling reactions
of Grignard reagents with vinyl [9-–12] and allyl
halides [13, 14]. Fe(acac)3 the most commonly used in
the synthesis of natural compounds [15, 16] and drugs
[17–20] is advantageously characterized by low hygro-
scopicity, good solubility, and ease of handling [21].
Structure and purity of the obtained compounds
was confirmed by high-performance GLC analysis,
NMR spectroscopy and chromato-mass spectrometry.
A reliable evidence of the stereochemical configura-
tion of isomers 2a and 2b was the values of spin-spin
coupling constant of vinyl hydrogen atoms (J = 15.6
and 11.3 Hz), characteristic of the E- and Z-con-
figurations, respectively. In addition, the signal of the
The reaction of (E)-1,3-dichloropropene la with
3 equiv of PhMgBr in tetrahydrofuran in the presence
of 3 mol % of Fe(acac)3 afforded a mixture of (E)- and
(Z)-isomers of 1,3-diphenylpropene 2a and 2b (E : Z =
Scheme 1.
MgBr
Fe(acac)3, _35oC
+
Cl
Cl
THF
(E)-1а, (Z)-1b
(E)-2а, (Z)-2b
342

343
A SIMPLE SYNTHESIS OF 1,3-DIPHENYLPROPENE
allylic carbon atom of trans-isomer 2a was shifted
downfield by ~5 ppm compared with the cis-analog 2b.
temperature programming mode from 50 to 300°C at a
rate of 10 deg/min, carrier gas helium (1.1 mL/min)].
Cross-coupling of (E)-1,3-dichloropropene with
PhMgBr. To a solution of 0.1 g (0.9 mmol) of (E)-1,3-
dichloropropene 1a, 9.5 mg (0.027 mmol) of Fe(acac)3
in 1 mL of THF in an argon atmosphere at –35°C was
slowly added 2.7 mL of a 1 M solution of PhMgBr in
THF. The reaction mixture was stirred at –35°C for
1.5 h, and then treated with a 10% HCl solution and
3 mL of hexane. The organic layer was separated, and
the aqueous layer was extracted with hexane (3 × 3 mL).
The combined organic phases were washed with a
saturated NaHCO3 solution, dried with MgSO4, and
concentrated. The reaction products were isolated by
column chromatography (SiO2, hexane). Yield 0.129
(2a) and 0.011 g (2b).
ACKNOWLEDGMENTS
This work was financially supported by the
Ministry of Education and Science of Russia within
the framework of the basic part of the governmental
task (no. 4.6451.2017/8.9).
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