Indium(I)/CuFe2O4 Reagent for Allylation of Carbonyls and Epoxide Rearranged Carbonyls

Article abstract of DOI:10.1134/S1070363220110274

Abstract: Indium(I)/CuFe₂O₄ reagent forcarbonyl allylation and epoxide rearranged carbonyl allylation is proposed forformation of homoallylic alcohols. The In(I) reagent in combination withcatalytic amount of CuFe₂O₄support in situ formation of nucleophilicallylic indium from allyl halide in THF medium. Nucleophilic allylic indiumspecies react with carbonyls to form homoallyl alcohols in good to excellentyields. Under the presented reaction conditions arylepoxides undergo smoothrearrangement into aldehydes that are also allylated with formation of homoallylalcohols. The process is highly efficient and tolerates different functionalgroups.

Full text of DOI:10.1134/S1070363220110274

ISSN 1070-3632, Russian Journal of General Chemistry, 2020, Vol. 90, No. 11, pp. 2189–2196. © Pleiades Publishing, Ltd., 2020.
Indium(I)/CuFe O Reagent for Allylation of Carbonyls
2
4
and Epoxide Rearranged Carbonyls
a
a
a,b,
a
M. Kundu , S. P. Mandal , B. Mondal *, and U. K. Roy
a
Department of Chemistry, Kazi Nazrul University, Asansol, 713340 India
Department of Chemistry, National Institute of Technology Durgapur, Durgapur, 713209 India
e-mail: uroccu@gmail.com
b
*
Received August 13, 2020; revised September 10, 2020; accepted October 2, 2020
Abstract—Indium(I)/CuFe O reagent for carbonyl allylation and epoxide rearranged carbonyl allylation is pro-
2
4
posed for formation of homoallylic alcohols. The In(I) reagent in combination with catalytic amount of CuFe O4
2
support in situ formation of nucleophilic allylic indium from allyl halide in THF medium. Nucleophilic allylic
indium species react with carbonyls to form homoallyl alcohols in good to excellent yields. Under the presented
reaction conditions arylepoxides undergo smooth rearrangement into aldehydes that are also allylated with forma-
tion of homoallyl alcohols. The process is highly efficient and tolerates different functional groups.
Keywords: indium(I)chloride, catalyst, copper ferrite, carbonyl allylation, arylepoxides, homoallylic alcohols
DOI: 10.1134/S1070363220110274
INTRODUCTION
follow-up reductive elimination affords allylindium(III)
derivatives. The overall reaction may be interpreted as
a redox transmetallation. It is noteworthy that indium(I)
halide (In-Xʹ) may be used directly or generated in situ
by mixing indium metal and an indium trihalide.
Allyl indium compounds bearing the C-In bond are the
most widely used indium compounds in organic synthesis
1]. Among their unique properties is tolerance towards
[
water. Allyl indium derivatives in situ were generated
by reductive transmetallation of allyl transition metal
complexes that could be accumulated from allyl bromide
and transition metal catalysts in combination with In(0)
and In(III) chloride. These are efficient nucleophilic
partners in different multicomponent allylation reactions
with a variety of electrophilic reagents [2, 3]. Such
reactions lead to the new C–C bonds formation with the
desired regio- and stereo-selectivity, that are of particular
importance in synthesis of various natural compounds
The above strategy for the Barbier allylation of
aldehydes using InI and catalytic amount of Pd(PPh ) in
organic solvent leads to formation of homoallylic alcohols
with high regioselectivity and varying diastereoselectivity
3
4
[8, 9]. Such strategy has been extended to the regioselective
allylation of aldehydes in aqueous-organic medium using
Scheme 1. Generation of allylindium.
[
4–7].
Allyl halides, their derivatives, as well as allenes and
dienes are easily activated by a reactive Tm(0) catalyst
Tm = Pd, Ni) to give rise to the corresponding π-allyl-
(
Tm(II) intermediates.Allyl transfer from the latter to In(I)
or In(0) generates reactive allylindium intermediates,
that are utilized in situ for the subsequent C–C bond
formation. The allylindium species react with carbonyl
compounds to give the corresponding homoallyl alcohols.
Oxidative addition of allyl halides, esters, carbonates,
ethers, cyclic amines, and alcohols to Pd(0) leads to well-
known π-allylpalladium(II) intermediates (Scheme 1).
Subsequent insertion of In(I) halides provides the
II
III
corresponding π-allyl-Pd –In intermediates. The
2
189

2190
KUNDU et al.
Scheme 2. Generation and reactivity of some allylindium derivatives.
in situ generated InCl [10]. We tried other transition metal
catalysts, especially copper catalysts, in such processes.
Magnetically separable copper ferrite was found to be
the most suitable for the Barbier type allylation reactions.
was the most efficient in formation of homoallyl alcohol
via in situ generation of allyl-nucleophile allylindium.
Our study was started with the reaction of allyl
bromide and aromatic aldehyde with indium and indium
trichloride. Unfortunately, the very first test reaction of
The magnetically separable CuFe O catalyst was
2
4
3
-bromopropene 1a and 4-chlorobenzaldehyde 2a with
utilized for the in situ synthesis of allylindium derivatives
Scheme 2). The transition metal complex “[Tm]” and
in situ generated InCl from the equivalent amounts of
indium and indium trichloride in dry DCM failed to give
any product. Amere switch of the solvent system to THF
led to less than 25% of the desired homoallylic alcohol
(
allyl-moiety were supposed to generate “allyl-[Tm]”.
The in situ generation of allyl-indium may be interpreted
as the redox-transmetallation process involving allyl
transfer from “allyl-[Tm]” to In(0/I) ensuring catalytic
regeneration of the [Tm] reagent (Scheme 2). The “allyl-
indium” intermediate generated via the above pathway
can act further as a source of allyl-nucleophile in the
following carbon-carbon bond formation. For such allyl-
nucleophiles a range of electrophiles including epoxides,
imines and carbonyls were tested in the carbon-carbon
bond formation.
3
a. Use of MeCN solvent resulted in only 15% yield
of 3a. Most remarkably, addition of catalytic amount
of CuCl ·2H O (1 mol % with respect to the carbonyl)
promoted a facile reaction which gave 3a with 66% yield.
The reaction carried out under same conditions but in
presence of cationic complex Cu(OTf) led to 68% yield
of 3a. The highest yield of 3a was achieved by using
the magnetically separable catalyst CuFe O . These
preliminary results clearly supported our view on the
2
2
2
2
4
RESULTS AND DISCUSSION
efficiency of organometallic processes activation by InCl.
Some carbon-carbon bond forming reactions have
been tried with the above synthesized magnetically
separable cationic, oxo- and some other complexes of
high valence iron and copper. Few commercially available
high valence iron and copper salts have also been tried.
It was determined that CuFe O catalyzed allylation of
Followingtheaboveapproachanumberofoptimization
experiments has been carried out (Table 1), and the
highlights of those are presented below.
9
10
(1) The d and d metal complexes of copper acted
as the most efficient catalysts in THF medium. These
catalysts were magnetically separable, thus adding the
advantage with respect to green chemistry approach.
2
4
aldehydes as well as arylepoxides rearranged aldehydes
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INDIUM(I)/CuFe O REAGENT FOR ALLYLATION OF CARBONYLS
2191
2
4
Table 1. InCl promoted carbonyl allylation: effect of catalysts and solvents
a
Run no.
X
Br
Catalyst (1 mol %)
NIL
NIL
NIL
Solvent
DCM
MeCN
THF
Time, h
Yield , %
1
2
3
4
5
6
7
8
9
9
9
9
9
9
9
9
9
9
9
Traces
15
25
25
66
68
76
73
64
Br
Br
Br
Br
Br
Br
Br
Br
Cl
NIL
THF–H O (9 : 1)
2
CuCl ·2H O
THF
THF
THF
THF
THF
THF
2
2
Cu(OTf)2
CuFe O
2
4
Cu Zn Fe O
4
0
.5
0.5
2
CuCl
CuFe O
1
0
54
2
4
a
Isolated yields after chromatography based on aldehydes.
(
2) Additives such as QPh (where Q = phosphorus,
the corresponding homoallylic alcohols was achieved
(entry 7).
3
arsenic, antimony) and dppe did not play any significant
roleinyieldimprovement.Thissuggestedthatcoordinative
unsaturation was necessary for initial activation of
electrophiles.
(2) The same method applied to the organometallic
substrate 2d yielded in a ferrocene derivative 3c with the
ene-terminal (entry 3).
(
3) Solvents played a very important role in the
(
2) Interestingly, in the reaction of benzene-1,4-
process.Among the tested solvents, THF was determined
as the best choice compared to DCM, MeCN, and THF–
H O.
dicarboxaldehyde 2h with 2-fold excess of allyl bromide,
the mono allylated product 3h (syn : anti = 53 : 47) was
obtained beside the desired bis allylated derivative 3i.
Compound 3h was of certain interest due to further
allylation at the bare –CHO terminal that could lead to
different homoallyl pendants at both sides of the phenyl
ring (entry 7).
2
The effect of water addition in promoting the reaction
was not prominent.
Allyl bromide was much more reactive compared to
allyl chloride. Activation of allyl alcohol in the presence
of Cu(II) or Cu(I) catalysts was inefficient.
(4)Attempted application of allyl halides with ketones
The above data (Table 1) indicated that the optimum
conditions were those presented in entry 7. This version
of the Barbier reaction was extended to a variety of
aldehydes and substituted allyl bromides for generating
homoallylic alcohols by the standard conditions
in the reaction was unsuccessful, thereby suggesting the
aldehyde-selectivity of the reagent. Such chemoselectivity
was not general for indium mediated carbonyl allylation.
The reaction conditions of carbonyl allylation could
be efficient in arylepoxide rearranged carbonyl allylation.
Indium chloride was supposed to be the Lewis acid and
under Lewis acidic conditions arylepoxides readily
underwent rearrangement towards carbonyls. Styrene
oxide 4a demonstrated epoxide rearrangement followed
by carbonyl allylation giving homoallyl alcohols 5a–5g,
(Scheme 3).
Several conclusions could be drawn from the
accumulated data (Table 2).
1) Allylation reaction was 100% γ-regioselective,
however the diastereoselectivity (syn : anti ratio) of
(
Scheme 3.
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2192
KUNDU et al.
Table 2. Allylation of carbonylsa
Run
Product
no.
b
Syn : antic
Halide
no.
Carbonyl
Product
Yield , %
1
3a
76
–
2
3b
3c
75
–
–
3
FcCHO
68
4
5
PhCH CHO
3d
3e
58
53
–
–
2
Me(CH ) CHO
2
6
6
7
3f
74
–
OH
Me
Me
3g
Mono-ol 27
Diol 42
53 : 47
46 : 54
OH
Me
OHC
8
3h
70
–
OH
O
Me
OEt
a
b
c
Carbonyl (1 mmol), allyl bromide (2 mmol), In (1 mmol), InCl (1 mmol), CuFe O (1 mol %), THF (2 mL), 40°C.
3
2
4
Isolated yield after column chromatography.
1
Determined by H NMR.
that corresponded allylation of phenyl acetaldehyde under
the above mentioned reaction conditions (Scheme 4).
In all cases, homoallylic alcohols were obtained as
the exclusive or major products due to the attack of
allyl nucleophiles to epoxide rearranged aldehydes.
Reactions with substituted allyl bromides demonstrated
exclusive γ-regioselectivity (Table 3, entries 3–5, 7). The
The above new version of the Barbier reaction was
extended to a variety of arylepoxides and substituted allyl
bromides for generating homoallylic alcohols under the
above standard conditions.
1
,2-diastereoselectivity (syn-anti ratio) was poor and
varied from substrate to substrate (Table 3, entries 2, 3).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

INDIUM(I)/CuFe O REAGENT FOR ALLYLATION OF CARBONYLS
2193
2
4
Scheme 4.
EXPERIMENTAL
preparations and manipulations were carried out under the
inert atmosphere of Ar using standard vacuum lines and
Schlenk techniques.All drying and distillation procedures
were carried out according to the standard methods and
previously deoxygenated in the vacuum line. Pre-coated
The chemicals used were either commercial products
Aldrich, Lancaster, Fluka, Merck, SRL, Spectrochem).
Those were distilled or recrystallized whenever required,
or prepared according to literature procedures. All
(
Table 3. Allylation of epoxidesa
Run
no.
1
Product
no.
Time, Yieldb,
Halide
Epoxide
Product
syn : antic
h
%
5a
11
75
–
2
3
5b
5c
13
13
78
68
63 : 37
40 : 60
4
5
5d
5e
12
3
72
47
–
–
6
7
5f
14
85
–
–
5g
13
38
a
b
c
Conditions: epoxide (1 mmol), allyl bromide (2 mmol), In (1 mmol), InCl (1 mmol), CuFe O (1 mol %), THF (2 mL), 40°C.
3
2
4
Isolated yield after column chromatography.
1
Determined by H NMR.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

2194
KUNDU et al.
silica gel 60F254 (Merck) plated were used for TLC, and
silica gel 60–120 and 100–200 mesh (SRL) was used for
with diethyl ether (3×10 mL), washed with water (2×
10 mL), brine (2×10 mL), and dried over magnesium
sulfate. After column chromatography (gradient elution
starting from ethyl acetate–hexane, 2 to 10%) the solvent
was evaporated to give the corresponding homoallylic
alcohols (3a–3h).
1
13
column chromatography. H (200 MHz) and C NMR
54.6 MHz) spectra were measured on a Brucker-AC 200
(
MHz spectrometer using TMS as an internal standard and
CDCl as a solvent. ESI-MS and HRMS spectra were
3
measured on a Waters LCT mass spectrometer. Elemental
analyses were performed on a Perkin Elmer 2400 Series
II CHNS/OAnalyzer and Vario EL, Elementar. Reactions
were monitored by TLC.
Synthesis of homoallylic alcohols by tandem
epoxide rearrangement-allylation. To a stirred solution
of epoxide (1 mmol), mmol) in THF (2 mL), In (1 mmol)
and InCl (1 mmol) were added slowly and the mixture
3
Synthesis of magnetically separable catalysts. The
was stirred for 5 min at a 40°C. Then, allyl bromide
(2 mmol) and CuFe O (1 mol %) were added. After
nanocrystalline CuFe O and Zn substituted CuFe O
2
4
2
4
2
4
[
Cu Zn Fe O ] were prepared by the chemical co-
completion of the reaction (TLC) water was added to
the mixture followed by ammonium fluoride, and it
was extracted by ethyl acetate. The combined organic
layers were washed with water (4×50 mL), brine and
0
.5
0.5
2
4
precipitation method. CuCl ·2H O, FeCl And ZnCl
were used as the precursors. For preparing CuFe O
the required amount of CuCl ·2H O was mixed with
2
2
3
2
2
4
2
2
FeCl and 200 mL of triple distilled water. The mixture
3
dried over anhydrous MgSO . The solvent was removed
4
was ultrasonicated for about 2 h. The solution of NaOH
in triple distilled water was added drop wise to the
solution of salts to make pH of the solution to be ca
under reduced pressure, and the following column
chromatography (silica gel 60–120, eluent—2% ethyl
acetate in hexane) gave the corresponding allylated
product (5a–5g).
1
0. Ultrasonication was carried on for another 1 h. The
co-precipitated particles were rigorously stirred by a
magnetic stirrer at 60°C for 2 h then filtered off and
washed repeatedly by triple distilled water to reach neutral
pH and remove the extra ions. The filtered particles were
dried at 80°C for 24 h. For preparing Cu Zn Fe O
1
-(4-Chlorophenyl)but-3-en-1-ol (3a) [11, 12]. Yield
1
7
4
7
7
6%. Н NMR spectrum, δ, ppm: 2.42–2.51 m (2H),
.67–4.73 m (1H), 5.09–5.2 m (2H), 5.67–5.88 m (1H),
.2–7.34 m (1H). C NMR spectrum, δ , ppm: 43.81,
2.62, 118.76, 127.25, 128.54, 133.15, 134.01, 142.34.
13
С
0
.5
0.5
2
4
the required amount of CuCl ·2H O was mixed with
2
2
Found, %: C 65.69, H 6.03. C H ClO. Calculated, %:
1
0
11
iron chloride and zinc chloride followed by addition of
50 mLof triple distilled water. Thus prepared solution of
CuCl ·2H O, ZnCl and FeCl was ultrasonicated for ca
C 65.76, H 6.07.
-Phenylbut-3-en-1-ol (3b) [12, 13]. Yield 75%. Н
NMR spectrum, δ, ppm: 2.12 br. s (1H), 2.48–2.56 m (2H),
.74 t (1H, J = 6.4 Hz), 5.12–5.21 m (2H), 5.72–5.92 m
2
1
1
2
2
2
3
2
h. Solution of NaOH in triple distilled water was added
4
(
4
1
drop wise to the solution of salts upon ultrasonication
to achieve pH 10 and ultrasonication was carried on for
another 1 h. The co-precipitated particles were rigorously
stirred by a magnetic stirrer at 60°C for 2 h. The co-
precipitated particles were then filtered off and washed
repeatedly by triple distilled water to neutralize pH
and remove the extra ions. The filtered co-precipitated
particles were collected by vacuum filtration and dried
at 80°C for 24 h.
1
3
1H), 7.23–7.38 m (5H). C NMR spectrum, δ , ppm:
3.85, 73.34, 118.41, 125.84, 127.57, 128.44, 134.48,
43.9. Found, %: C 81.09, H 8.20. C H O. Calculated,
С
1
0
12
%
: C 81.04, H 8.16.
2,2-Dimethyl-1-ferrocenylbut-3-en-1-ol (3c). Yield
68%. Н NMR spectrum, δ, ppm: 0.92 s (3H), 0.96 s
(3H), 2.15 br. s (1H, OH), 4.00 s (1H), 4.19 s (9H), 4.92–
5.04 m (2H), 5.79–5.93 m (1H). C NMR spectrum, δС,
1
1
3
ppm: 22.15, 23.76, 41.37, 65.67, 67.42, 67.61, 68.34,
Allylation of carbonyl compounds using InCl and
3
+
6
9.79, 77.15, 112.35, 145.39. EIMS: m/z: 284 [M] .
CuFe O catalysis. To a mixture of a carbonyl compound
2
4
Found, %: C 67.35, H 7.11. C H OFe. Calculated, %:
(
1 mmol) with allyl bromide (2 mmol) in THF (2 mL)
16 20
C 67.61, H: 7.04.
In (1 mmol), InCl (1 mmol) and CuFe O (1 mol %)
3
2
4
were added slowly in the atmosphere of Ar. The mixture
was stirred at 40°C for 8–9 h. (TLC monitoring on silica
gel, eluent—n-hexane : ethyl acetate, 9 : 1). An aqueous
solution of ammonium fluoride (15%, 10 mL) was added
to the reaction mixture and organic layer was extracted
1-Phenylpent-4-en-2-ol (3d) [12, 14, 15]. Yield 58%.
Н NMR spectrum, δ, ppm: 1.81 br. s (1H), 2.23–2.36 m
1
(2H), 2.67–2.86 m (2H), 3.86–3.93 m (1H), 5.13–5.21 m
(2H), 5.78–5.90 m (1H), 7.22–7.37 m (5H). 13C NMR
spectrum, δ , ppm: 41.22, 43.34, 71.75, 118.13, 126.51,
С
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INDIUM(I)/CuFe O REAGENT FOR ALLYLATION OF CARBONYLS
2195
2
4
1
8
28.57, 129.48, 134.75, 138.46. Found, %: C 81.38, H
.67. C H O. Calculated, %: C 81.44, H 8.70.
(1H, OH), 4.18 m (2H), 5.02–5.12 m (2H), 5.73–5.90 m
1
3
(1H). C NMR spectrum, δ , ppm: 14.09, 26.75, 44.23,
11
14
С
4
6.43, 60.45, 70.57, 118.40, 133.61, 172.75.
Phenyl-1-undecen-4-ol(3e)(syn:anti=0:100). Yield
3%. Н NMR spectrum, δ, ppm: 0.85 t (3H, J = 5.5 Hz),
.22–1.42m(12H),1.62br.s(1H,–OH),3.24m(1H),3.78m
1
5
1
(
1-Phenylpent-4-en-2-ol (5a) [12, 14, 15]. Yield 75%.
1
Н NMR spectrum, δ, ppm: 1.75 br. s (1H), 2.15–2.39 m
(2H), 2.67–2.88 m (2H), 3.82–3.93 m (1H), 5.12–5.22 m
(2H), 5.77–5.94 m (1H), 7.15–7.37 m (5H). 13C NMR
1H), 5.09–5.24 m (2H), 6.03–6.17 m (1H), 7.19–7.42 m
13
(
5H). C NMR spectrum, δ , ppm: 14.06, 22.62, 25.71,
С
2
1
1
9.22, 29.51, 31.80, 34.46, 57.38, 74.27, 117.76, 126.62,
28.03, 128.55, 138.40, 141.78. Found, %: C 82.75, H
0.69. C H O. Calculated, %: C 82.87, H 10.64.
spectrum, δ , ppm: 41.18, 43.29, 71.68, 118.14, 126.48,
С
1
28.53, 129.42, 134.68, 138.37. ESI-MS: 145.108 [M –
+
17
26
OH] . Found, %: C 81.68, H 8.51. C H O. Calculated,
11 14
2
,2 Dimethyl-1-phenylbut-3-en-1-ol (3f) [12, 16].
%: C 81.44, H 8.70.
1
Yield 74%. Н NMR spectrum, δ, ppm: 0.97 s (3H), 1.02 s
3H), 4.43 s (1H), 5.04–5.18 m (2H), 5.85–6.00 m (1H),
.26–7.32 m (5H). C NMR spectrum, δ , ppm: 21.12,
4.48, 42.28, 80.71, 113.83, 127.44, 127.51, 127.82,
40.84, 145.14. Found, %: C 81.79, H 9.19. C H O.
2
-Phenylhex-5-en-3-ol (5b) (syn : anti = 63 : 37) [18].
(
7
2
1
1
Yield 78%. Н NMR spectrum, δ, ppm: 1.26 d, 1.35 d [3H,
J = 6.8 Hz each (anti+syn)], 1.7 br. s (1H), 1.99–2.25 m
1
3
С
(2H), 2.75–2.82 m (1H), 3.68–3.77 m (1H), 5.06–5.18 m
1
2
16
(
1
2H), 5.73–5.87 m (1H), 7.20–7.36 m (5H). ESI-MS:
59.117 [M – OH] . Found, %: C 81.69, H 9.20. C H O.
Calculated, %: C 81.77, H 9.15.
+
1
2
16
4
-(1-Hydroxy-2-methylbut-3-enyl) benzaldehyde
Calculated, %: C 81.77, H 9.15.
1
(
(
(
5
(
3g) (syn : anti = 53 : 47). Yield 27%. Н NMR spectrum
anti isomer), δ, ppm: 0.94 d (3H, J = 8.0 Hz), 2.29–2.58 m
1H), 4.46 d (1H, J = 7.5 Hz), 5.02–5.22 m (2H), 5.72–
.81 m (1H), 7.41–7.52 m (2H), 7.82–7.88 m (2H), 9.99 s
1H). H NMR spectrum (syn isomer), δ, ppm: 0.98 d (3H,
J = 8.0 Hz), 2.29–2.58 m (1H), 4.73 d (1H, J = 7.5 Hz),
.02–5.22 m (2H), 5.72–5.81 m (1H), 7.41–7.52 m (2H),
.82–7.88 m (2H), 9.99 s (1H). C NMR spectrum, δ ,
ppm: 13.93, 16.29 (anti+syn); 44.57, 46.22 (anti+syn);
3-Methyl-1-phenylpent-4-en-2-ol (5c) [19, 20] (syn :
1
anti = 40 : 60). Yield 68%. Н NMR spectrum, δ, ppm:
.12 d, 1.21 d [3H, J = 6.7 Hz each (anti+syn)], 1.65 br. s
1
(
(
(
1H), 2.30–2.37 m (1H), 2.55–2.69 m (1H), 2.83–2.93 m
1H), 3.67–3.75 m (1H), 5.09–5.18 m (2H), 5.79–5.96 m
1H), 7.18–7.36 m (5H). C NMR spectrum, δ , ppm:
1
1
3
С
5
7
1
4
4. 54, 16.33 (anti+syn); 40.76, 40.81 (anti+syn); 43.01,
3.23 (anti+syn); 75.64, 75.74 (anti+syn); 115.24,
1
3
С
116.08 (anti+syn); 126.31, 126.77 (anti+syn); 128.43,
7
1
(
6.54, 77.24 (anti+syn); 116.39, 117.46 (anti+syn);
27.01, 127.37 129.50, 129.63 (anti+syn); 139.57, 139.66
anti+syn); 149.37, 149.49 (anti+syn); 191.93. EIMS:
1
28.47 (anti+syn); 129.28, 129.32 (anti+syn); 138.88,
1
38.94 (anti+syn); 139.87, 140.9 (anti+syn). ESI-MS:
+
+
·
159.097 [M – OH] . Found, %: C 81.89, H 9.20. C12H16O.
m/z: 191 [M] .
Calculated, %: C 81.77, H 9.15.
1
-[4-(1-Hydroxy-2-methylbut-3-enyl) phenyl]-2-
3
,3-Dimethyl-1-phenylpent-4-en-2-ol (5d) [21].
methylbut-3-en-1-ol (3g) (syn : anti = 46 : 54). Yield
2%. Н NMR spectrum, (anti isomer), δ, ppm: 0.86 d
1
1
Yield 72%. Н NMR spectrum, δ, ppm: 1.12 s (6H),
4
(
4
(
1
1
.58 br. s (1H), 2.4–2.52 m (1H), 2.9 d. d (1H, J =
3.7 Hz, J = 1.7 Hz), 3.51 d. d (1H, J =10.6 Hz, J = 1.9
6H, J = 6.0 Hz), 1.25 br. s (2H, –OH), 2.40–2.58 m (2H),
.36 d (2H, J = 6.0), 4.99–5.24 m (4H), 5.65–5.79 m
2H), 7.25–7.30 m (4H). 1H NMR spectrum (syn isomer),
δ, ppm: 1.00 d (6H, J = 6.0 Hz), 1.10 br. s (2H, –OH),
.40–2.58 m (2H), 4.62 d (2H, J = 6.0), 4.99–5.24 m
Hz), 5.06–5.15 m (2H), 5.87–6.01 m (1H), 7.21–7.35 m
1
3
(
5H). C NMR spectrum, δ , ppm: 22.79, 38.38, 41.46,
С
7
9.34, 113.05, 126.26, 128.48, 129.3, 139.88, 145.2.
2
(
+
1
3
ESI-MS: 173.13 [M – OH] . Found, %: C 81.98, H 9.49.
C H O. Calculated, %: C 82.06, H 9.53.
13 18
4H), 5.65–5.79 m (2H), 7.25–7.30 m (4H). C NMR
spectrum, δ , ppm: 13.96, 16.45 (anti+syn); 29.63, 31.15
С
(
(
(
(
anti+syn); 44.59, 46.23 (anti+syn), 115.47, 116.76
anti+syn); 125.49, 125.67 (anti+syn); 126.34, 126.51
3-Methylene-5-(1-phenylethyl)-dihydrofuran-2-
one (5e) [22] Yield 47%. Н NMR spectrum, δ, ppm:
.41–1.44 d (3H, J = 7 Hz), 2.49–2.74 m (2H), 2.77–2.92 m
1
anti+syn); 126.68, 126.79 (anti+syn); 140.22, 140.57
1
+
anti+syn). EIMS: m/z: 210 [M – 2H O] .
2
(1H), 4.53–4.64 m (1H), 5.49–5.52 m (1H), 6.14–6.17 m
1
3
3
-Hydroxy-3-methyl-5-hexenoic acid ethyl ester
(1H), 7.17–7.37 m (5H). C NMR spectrum, δ , ppm:
С
1
(
1
3h) [17]. Yield 70%. Н NMR spectrum, δ, ppm:
.23–1.37 m (6H), 2.26 m (2H) 2.42 m (2H), 3.61 br. s
17.88, 31.91, 45.54, 81.11, 121.77, 127.10, 127.75,
+·
128.69, 134.51, 141.31, 170.22. EIMS: m/z: 202 [M] .
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020

2196
KUNDU et al.
Found, %: C 76.65, H 7.14. C H O . Calculated, %: C
5. Hirashita, T., Takahashi, F., Noda, T., Takagi, Y., and
Araki, S., Molecules, 2018, vol. 23, p. 1696.
1
3
14
2
7
7.20, H 6.98.
-Anthrylpent-4-en-2-ol (5f). Yield 85%. Н NMR
spectrum, δ, ppm: 1.72 br. s (1H), 2.42–2.48 m (2H),
.79–3.83 m (2H), 4.12–4.15 m (1H), 5.16–5.26 m
2H), 5.84–5.93 m (1H), 7.42–7.56 m (4H), 7.97–8.02 m
https://doi.org/10.3390/molecules23071696
1
1
6
.
Gordon, D.M. and Whitesides, G.M., J. Org. Chem.,
993, vol. 58, p. 7937
https://doi.org/10.1021/jo00079a050
1
3
(
(
7. Chan, T.H. and Lee, M.C., J. Org. Chem., 1995,
vol. 60, p. 4228.
1
3
2H), 8.28–8.36 m (3H). C NMR spectrum, δ , ppm:
С
https://doi.org/10.1021/jo00118a044
3
4.74, 41.93, 72.18, 118.40, 124.64, 124.89, 125.71,
8
9
1
.
Araki, S., Kamei, T., Hirashita, T., Yamamura, H., and
Kawai, M., Org. Lett., 2000, vol. 2, p. 847.
https://doi.org/10.1021/ol005610i
Hirashita, T., Kamei, T., Satake, M., Horie, T., Shimizu, H.,
and Araki, S., Org. Biomol. Chem., 2003, vol. 1, p. 3799.
https://doi.org/10.1039/B306195G
1
2
26.57, 129.17, 130.53, 130.62, 131.52, 134.74. ESI-MS:
+
63.14 [M + H] . Found, %: C 86.92, H 6.76. C H O.
1
9
18
Calculated, %: C 86.99, H 6.92.
.
4
-Methyl-1-phenylpent-4-en-2-ol (5g) [23]. Yield
1
3
8%. Н NMR spectrum, δ, ppm: 1.75 s (3H), 1.81 br. s
0. Jang, T.S., Keum, G., Kang, S.B., Chung, B.Y., and
Kim, Y., Synthesis, 2003, p. 775.
(
(
1H), 2.16–2.29 m (2H), 2.76–2.79 m (2H), 3.93–4.02 m
1H), 4.82–4.95 m (2H), 7.2–7.46 m (5H). C NMR
1
3
https://doi.org/10.1055/s-2003-38059
spectrum, δ , ppm: 22.38, 43.50, 45.43, 69.84, 113.48,
С
11. Kundu, A., Prabhakar, M., Vairamani, M., and Roy, S.,
1
26.4, 127.85, 128.43, 139.90, 142.57. ESI-MS: 159.10
Organometallics, 1999, vol. 16, p. 4796.
https://doi.org/10.1021/om9704096
+
[
M – OH] . Found, %: C 81.81, H 9.26. C H O.
12 16
Calculated, %: C 81.77, H 9.15.
1
2. Sinha, A. K., Mondal, B., Kundu, M., Chakraborty, B., and
Roy, U. K. Org. Chem. Front., 2014, vol. 1, p. 1270.
https://doi.org/10.1039/c4qo00235k
CONCLUSIONS
We have demonstrated a facile allylation of carbonyl
and arylepoxide compounds using In–InCl and CuFe O
catalyst in the synthesis of homoallyl alcohols with
two carbon extensions, that is expected to enrich the
synthetic application of the reaction. Further study of the
mechanism of the process is warranted.
13. Barczak, N.T., Grote, R.E., and Jarvo, E.R., Organo-
metallics, 2007, vol. 26, p. 4863.
3
2
4
https://doi.org/10.1021/om700605y
1
1
4. Roy, U.K. and Roy, S., Tetrahedron, 2006, vol. 62, p. 678.
https://doi.org/10.1016/j.tet.2005.10.005
5. Banerjee, M., Roy, U.K., Sinha, P., and Roy, S., J. Organo-
met. Chem., 2005, vol. 690, p. 1422.
https://doi.org/10.1016/j.jorganchem.2004.12.008
6. Hayashi, S., Hirano, K., Yorimitsu, H., and Oshima, K.,
Org. Lett., 2005, vol. 7, p. 3577.
https://doi.org/10.1021/ol0515199
17. Araki, S., Ito, H., and Butsugan, Y., J. Org. Chem.,
1988, vol. 53, p. 1831.
FUNDING
1
Financial support of this work by SERB-New Delhi, SR/FT/
CS-137/2011 dated 12.07.2012, and Science and Technology
and Biotechnology-WB, 50(Sanc.)/ST/P/S&T/15G-10/2018
dated 30.01.2019 to UKR is gratefully acknowledged.
https://doi.org/10.1021/jo00243a052
8. Jiang, N., Hu, Q., Reid, C.S., Lu, Y., and Li, C.-J., Chem.
Commun., 2003, p. 2318.
https://doi.org/10.1039/B305161G
9. Collins, S., Kuntz, B.A., and Hong, Y., J. Org. Chem.,
CONFLICT OF INTEREST
No conflict of interests was declared by the authors.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 11 2020