Ruthenium(iii)-catalysed phenylselenylation of allyl acetates by diphenyl diselenide and indium(i) bromide in neat: Isolation and identification of intermediate

Article abstract of DOI:10.1039/c0ob00317d

A fast and efficient phenylselenylation of allyl acetates by diphenyl diselenide and indium(i) bromide has been achieved in neat under the catalysis of Ru(acac)₃. The intermediate complex of diphenyl diselenide and indium has been isolated and identified as a polymeric pentacoordinated In(iii) selenolate complex, [In(SePh)₃]_n.

Full text of DOI:10.1039/c0ob00317d

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PAPER
Ruthenium(III)-catalysed phenylselenylation of allyl acetates by diphenyl
diselenide and indium(I) bromide in neat: isolation and identification of
intermediate†
Amit Saha and Brindaban C. Ranu*
Received 25th June 2010, Accepted 24th November 2010
DOI: 10.1039/c0ob00317d
A fast and efficient phenylselenylation of allyl acetates by diphenyl diselenide and indium(I) bromide
has been achieved in neat under the catalysis of Ru(acac)3. The intermediate complex of diphenyl
diselenide and indium has been isolated and identified as a polymeric pentacoordinated In(III)
selenolate complex, [In(SePh)3]n.
diselenide in the presence of InBr and Ru(acac)3 in neat (Scheme 1)
to provide allyl phenyl selenide.
Introduction
Allyl selenides have received considerable attention in recent times
because of their importance as versatile synthetic intermediates.1
Allyl selenides undergo [2,3] sigmatropic rearrangement under
a variety of conditions to provide allylic amines,2 halides3 and
alcohols.4 The organic selenium compounds also display sig-
nificant potential as anticancer and antioxidant agents.5 Thus,
Scheme 1 Phenylselenylation of allyl acetates.
development of efficient procedures for the synthesis of allyl
selenides are of much importance. The traditional method for
their synthesis involves a nucleophilic substitution of allyl halides
Results and discussion
with phenylseleno anion.1,6 However, easily accessible, moderately
active and configurationally stable7 allyl acetates are more attrac-
tive. Surprisingly, only a limited number of methods using allyl
acetates are available. Huang et al.8 reported phenylselenylation
of allyl acetates by phenyl selenium bromide using Pd(PPh3)4 and
SmI2 although the yields of products are not satisfactory (47–
58%). A similar method using diphenyl diselenide in presence
of Pd(PPh3)4/SmI2 showed some improvement (47–84% yields).9
However, a major drawback of this reaction is the loss of
one equivalent of PhSe- as waste. The methods using diphenyl
diselenide in presence of La/Me3SiCl/I2/CuI in CH3CN10a and
To optimize the reaction conditions, a series of experiments were
carried out for a representative reaction of cinnamyl acetate and
diphenyl diselenide under varying reaction parameters such as
catalyst, solvent, reaction temperature etc (Table 1). It was found
that a combination of Ru(acac)3 and InBr in neat provides a fast
and efficient reaction (Table 1, entry 11). Other ruthenium catalysts
such as RuCl3 (Table 1, entry 1), RuCl2(PPh3)3 (Table 1, entry
14), [Ru(CO)3Cl2]2 (Table 1, entry 15), [(C6H6)RuCl2]2 (Table 1,
entry 16), Ru3(CO)12 (Table 1, entry 17) and Ru(0) nanoparticles
(Table 1, entry 2) are not very efficient. Although the Ru(II)
catalysts (Table 1, entries 14, 15 and 16) are moderately active,
the Ru(0) catalysts (Table 1, entries 2 and 17) are less active. The
use of solvents has a retarding effect on this reaction. Only THF
leads to a relatively good yield (36%). Other reducing agents to
cleave diphenyl diselenide such as Zn dust and InI are also not as
efficient as InBr. The amount of Ru(acac)3 for an efficient reaction
has also been optimized to 5 mol%.
Thus, in a typical experimental procedure a mixture of allyl
acetate, diphenyl diselenide, InBr and Ru(acac)3 was heated at 60–
80 ◦C for a period of time as required to complete the reaction
(TLC). Standard work-up followed by purification by column
chromatography provided the pure product.
A series of substituted cinnamyl acetates underwent coupling
with diphenyl diselenide by this procedure to produce the corre-
sponding selenides. The results are summarized in Table 2. For
10b
PhSeSiMe3 in the presence of ZnI2 had several disadvantages
with regard to efficiency (low yield), environmental acceptability
using toxic solvents like CH3CN and benzene and generality (only
3 examples). Thus, a convenient and efficient procedure for the
synthesis of allyl phenyl selenides is highly desirable. Recently
Tunge11 reported an elegant synthesis of chiral cyclohexenyl phenyl
selenides through palladium catalyzed decarboxylative coupling.
In this paper we report a coupling of allyl acetate and diphenyl
Department of Organic Chemistry, Indian Association for the Cultivation
of Science, Jadavpur, Kolkata, 700032, India. E-mail: ocbcr@iacs.res.in;
Fax: +91 33 24732805
† Electronic supplementary information (ESI) available: 1H NMR and
13C NMR spectra of all allyl selenides listed in Table 2. See DOI:
10.1039/c0ob00317d
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Table 1 Standardisation of reaction conditions
RuCl3. Interestingly, there are several reports of phenylselenylation
of alkyl halides including allyl bromides with diphenyl diselenide
using Zn dust only (for the cleavage of PhSeSePh) and without the
use of any transition metal catalyst including Ru.19 Being curious
we repeated the phenylselenylation of allyl bromide by diphenyl
diselenide under Yu’s condition using Zn dust only and without
RuCl3. The reaction goes remarkably well giving 91% conversion.
On the other hand, the reactions of allyl acetates and diphenyl
diselenide did not go efficiently in absence of Ru-catalyst.
Reducing
Entry agent
Temp.
(◦C)
Yielda
(%)
Catalyst
Solvent
Time
1
2
3
4
5
6
7
8
InBr
InBr
InBr
InI
RuCl3
THF
THF
THF
THF
THF
Dioxane 100
DMF 120
Toluene 100
Neat
Neat
Neat
Neat
Neat
Neat
Neat
66
66
66
66
66
15 h
15 h
15 h
15 h
15 h
15 h
15 h
15 h
5 h
Trace
0
Ru NPb
To understand the reaction pathway we considered isolation
of the intermediate. As the reaction proceeds very fast in neat
we have not been able to isolate any intermediate. However, as
the reaction proceeds in THF giving 36% yield (Table 1, entry 3)
we decided to check the reaction of cinnamyl acetate and diphenyl
diselenide in presence of InBr/Ru(acac)3 in THF. We are successful
to isolate a highly polar pale yellow solid from the reaction
mixture. The NMR spectrum revealed the presence of aromatic
protons. The X-Ray crystallographic analysis showed a polymeric
pentacoordinated indium-selenolate complex, [In(SePh)3]n, where
each indium center remains in a trigonal bipyramidal environ-
ment with one terminal SePh and two bridging SePh groups
(Fig. 1).20 This complex on reaction with cinnamyl acetate in
presence of Ru(acac)3/InBr under identical reaction conditions
produced the cinnamyl phenyl selenide in comparably high yield.
Thus, this observation unequivocally established the intermediacy
of [In(SePh)3]n in this reaction. Nevertheless, this intermediate
transfers SePh anion to allyl acetates in this reaction and this
complex was formed by the interaction of PhSeSePh and InBr
under the reaction conditions. In all reports14,21 of In(I)-mediated
cleavage of PhSeSePh, In(SePh)2I has been suggested as possible
intermediate and our results vacated this prediction and settled
this issue once for all.
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
Ru(acac)3
—
36
22
10
25
10
13
62
Zn dust
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
InBr
9
100
80
60
rt
60
60
60
60
60
10
11
12
13
14
15
16
17
10 min 77
10 min 90c
48 h
5 h
55
35d
RuCl2(PPh3)3
[Ru(CO)3Cl2]2
[(C6H6)RuCl2]2 Neat
Ru3(CO)12 Neat
10 min 61
10 min 58
10 min 55
10 min 38
a Isolated yields of pure products. b Ru NP = Ru nanoparticles prepared by
reducing RuCl3 by NaBH4 in MeOH. c 5 mol% of Ru(acac)3 was optimised
to give the best result. d Reaction was performed in absence of Ru(acac)3.
1 equivalent of allyl acetate 0.5 equivalent of PhSeSePh was
required for a complete reaction and thus two SePh moieties
were consumed making this reaction more atom economic. Both
electron-donating and electron-withdrawing substituents on the
aromatic ring are compatible with this reaction although the
electron-withdrawing substituted compounds took much longer
time [Table 2, entries 3 (120 min) and 4 (90 min)].
The reactions of all aryl substituted allyl acetates were accom-
plished at 60–80 ◦C within 5–20 mins (except those in entries 3 and
4, Table 2) by conventional heating whereas the reactions of alkyl
substituted allyl acetates remained incomplete by conventional
heating even for a prolonged period. However, microwave heating
produced much better results (Table 3). Thus reactions of all
alkyl substituted allyl acetates were carried out under microwave
irradiation. All linear and branched (Table 2, entries 9 and 15)
allyl acetates provided exclusively linear allyl phenyl selenides
through nucleophilic addition by organoselenium species from
the less hindered side. The trans-allyl acetates except crotyl acetate
(Table 2, entry 14) produced stereoselectively trans-selenides,
while cis-allyl acetates led to a mixture of cis and trans with
predominating trans isomer. Benzyl acetate having a partial allylic
character was also phenylselenylated efficiently (Table 2, entry 10).
In general, the reactions are clean and fast. The products
are obtained in high yields with good purity. Several functional
groups such as OMe, NO2, COMe, Cl, I are compatible with this
reaction. The reaction is uniform with o-, m-, and p- substituted
aryl allyl acetates. The palladium catalysts frequently used for
the phenylselenylation are prone to selenium poisoning. However,
the ruthenium catalyst used here is free from this drawback.
To the best of our knowledge this is the first report of use of
Ru-catalyst in phenylselenylation of allyl acetate, although Yu
et al.18 reported phenylselenylation of alkyl halides including allyl
bromide (one example) by diphenyl diselenide using Zn dust and
Fig. 1 Molecular view of intermediate [In(SePh)3]n.
To investigate the mechanism we carried out this reaction in
presence of TEMPO (Tetramethyl piperidine N-oxide) keeping
other reaction parameters unaltered. A marginal effect on rate of
conversion and yield was observed. Thus, it is unlikely that the
reaction is going through a radical pathway.
We propose an oxidative addition of Ru(II), generated in situ by
the reduction of Ru(III) by InBr,22 to allyl acetate resulting to a
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Table 2 Synthesis of allyl phenyl selenides
Entry
1
Allyl acetates
Product
Time (min)
5
Temp. (◦C)
60
Yielda (%)
Ref.
12
70
71
80
2
3
5
60
80
120
4
5
6
90
20
20
80
60
60
81
75
78
13
7
8
10
10
60
60
90
85
14
15
9
20
10
70
80
70
92
14
14
10b
11b
12b
20
20
100
100
75
72
16
17
13b,c
14b
20
20
95
93
94
14
14
100
15b
25
100
63
16
a Isolated yields of pure products. b Microwave irradiation at 200 watt. c Allyl acetate was used in 2 equivalents.
3
h -p-allyl complex, A or C which undergoes very fast trans-
metallation with [In(SePh)3]n followed by reductive elimination
to give the product (Scheme 2). The catalytic cycle involving
Ru(II) to Ru(IV) is very common in Ru catalyzed allylation
reactions.23 Our hypothesis of involvement of in situ generated
Ru(II) in the reaction gains support from the observation that three
commercially available Ru(II) catalysts also catalyse this reaction
producing the corresponding products (55–61%, Table 1, entries
14, 15 and 16) under identical reaction conditions. In case of
trans-allyl acetate we predict direct interaction of p-allyl complex
A with [In(SePh)3]n followed by reductive elimination to give the
trans product. However in case of cis-allyl acetate the complex
C, formed after the oxidative addition, having steric interaction
between a-H and g-R group is likely to equilibrate with A via
1
a h -s-alkyl complex B. Thus both the intermediates A and C
participate in the catalytic cycle to give the product as a mixture of
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Table 3 Comparison of results of reactions in conventional heating and microwave heating
Conventional heating
Microwave heating
Entry
1
Substrate
Time (h)
14
T/◦C
Yield (%) (E : Z)
Time (h)
0.3
Temp. (◦C)
Yield (%) (E : Z)
85
80
95
93
2
3
16
16
100
100
37 (74 : 26)
16 (90 : 10)
0.3
0.3
100
100
94 (80 : 20)
75 (80 : 20)
cantly, the selenium-indium intermediate complex, [In(SePh)3]n
formed during the cleavage of PhSeSePh by In(I) has been isolated
and characterized for the first time. This vacates the earlier
prediction of In(SePh)2I as possible intermediate in In(I)-mediated
cleavage of PhSeSePh. The other attractive features of this reaction
are novel use of Ru catalyst for the selenylation reaction, in-
volvement of air stable, commercially available diphenyl diselenide
and allyl acetate, high regioselectivity giving exclusively linear
selenides, excellent streoselectivity for trans allyl acetates, reaction
in neat in open atmosphere without requirement of any inert
gas and organic solvent, involvement of two SePh moieties of
diphenyl deselenide enhancing atom economy, very fast reaction
and high yields. Certainly this protocol shows greater promise
towards further useful applications.
Experimental section
Scheme 2 Proposed mechanistic pathway.
IR spectra were taken as thin films for liquid compounds and as
KBr pellets for solids on a FT-8300 Shimadzu spectrometer. NMR
spectra were recorded on a Bruker AVANCEIII 500 instrument at
500 MHz for 1H NMR and at 125 MHz for 13C NMR in CDCl3
solutions.
cis- and trans-allyl selenides. The transition state for the formation
of Ru-p-allyl complex is likely to become more stable by the p-
electron of the aromatic nucleus of aryl substituted allyl acetates
due to stabilization of the electron deficient Ru centre. Thus, the
reaction becomes faster in presence of electron donating group
(Me, OMe) on the aromatic ring of cinnamyl acetate, while rate
of the reaction becomes slow in presence of electron withdrawing
group (COMe, NO2). In case of branched aromatic allyl acetate
exclusively the linear allyl selenide was obtained as the product
Representative experimental procedure for the phenylselenylation
of cinnamyl acetate (entry 7, Table 2)
A mixture of cinnamyl acetate (1 mmol, 176 mg), diphenyl
diselenide (0.5 mmol, 156 mg), InBr (0.6 mmol, 117 mg) and
Ru(acac)3 (0.05 mmol, 5 mol%, 20 mg) was heated at 60 ◦C
for 10 min (TLC). After completion of the reaction the reaction
mixture was cooled, diluted with EtOAc (5 mL) and was filtered
to remove the metal residue. The solvent was evaporated under
reduced pressure. The crude product was purified by column
chromatography over silica gel (hexane–Et2O, 98 : 2) to furnish
the pure product as a white solid (245 mg, 90%). The compound
was identified as trans-cinnamyl(phenyl)selenide by comparison of
its mp and spectra (1H NMR and 13C NMR) with those reported
earlier.14
This procedure was followed for the reactions of all aryl-
substituted allyl acetates listed in Table 2 (entries 1 to 9). However,
for reactions of alkyl-substituted allyl acetates the reaction mixture
was heated under microwave irradiation (CEM, Discover model,
200 W) in place of conventional heating. All of these products
except four (Table 2, entries 1, 3, 4 and 6) are known and have
been identified by comparison of their spectroscopic data (IR, 1H
NMR and 13C NMR) with those reported (references in Table 2).
3
indicating the formation of a h -p-allyl complex followed by the
reductive elimination from the less hindered side of the allyl
complex. In case of R = alkyl group, the Ru-p-allyl complex does
not get enough stabilization due to absence of the aromatic ring
and the reaction becomes extremely slow. Thus, the reactions of
alkyl substituted allyl acetates proceeded faster under microwave
irradiation.24 From all these observations it may be concluded that
3
the formation of h -p-allyl complex is the rate determining step. In
case of trans-crotyl acetate (R = Me) the product was obtained as a
mixture of cis and trans-allyl selenide. This may be due to presence
of a less bulky Me group which makes complex A to equilibrate
with C producing a mixture of cis and trans-allyl selenide.
Conclusion
In conclusion, a simple and efficient Ru-catalyzed one pot proce-
dure for the phenylselenylation of allyl acetate involving diphenyl
diselenide and indium(I) bromide has been developed. Signifi-
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The unknown compounds (Table 2, entries 1, 3, 4 and 6) were
characterised properly by their spectroscopic data as follows:
11/2008] to B. C. Ranu. A. Saha is thankful to CSIR, New Delhi
for his fellowship. We sincerely thank the help of Mominul Sinan
of Inorganic Chemistry department for his help in solving the
crystal structure.
4-Methyl cinnamyl(phenyl)selenide (Table 2, entry 1)
Pale yellow viscous liquid; IR (neat) nmax/cm-1 3435, 3051, 3022,
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1
736, 688 cm-1; H NMR (CDCl3, 500 MHz) d 2.38 (s, 3H), 3.74
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Pale yellow liquid; IR (neat) nmax/cm-1 3057, 2926, 1577, 1527,
1
1477, 1437, 1350, 1072, 1020, 960, 898, 802, 732, 688 cm-1; H
NMR (CDCl3, 500 MHz) d 3.67 (d, J = 7.5 Hz, 2H), 6.19 (d, J =
15.5 Hz, 1H), 6.41–6.48 (m, 1H), 7.23–7.28 (m, 3H), 7.42 (t, J =
7.5 Hz, 1H), 7.51–7.54 (m, 3H), 8.03 (dd, J1 = 2.5 Hz, J2 = 8 Hz,
1H), 8.08 (s, 1H); 13C NMR (CDCl3, 125 MHz) d 30.3, 120.9,
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138.7, 148.7. Anal. Calcd for C15H13NO2Se: C, 56.61; H, 4.12; N,
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Pale yellow viscous liquid; IR (neat) nmax/cm-1 3028, 2924, 2852,
1741, 1676, 1602, 1479, 1438, 1406, 1359, 1269, 1224, 1182, 1070,
1020, 966, 827, 804, 732, 690 cm-1; 1H NMR (CDCl3, 500 MHz)
d 2.49 (s, 3H), 3.60 (d, J = 7.5 Hz, 2H), 6.13 (d, J = 15.5 Hz, 1H),
6.33–6.38 (m, 1H), 7.16–7.19 ((m, 3H), 7.25 (d, J = 8.5 Hz, 2H),
7.43–7.45 (m, 2H), 7.78 (d, J = 8 Hz, 2H); 13C NMR (CDCl3, 125
MHz) d 26.6, 30.6, 126.4 (3C), 127.7, 128.8 (2C), 129.1 (2C), 129.5,
131.0, 134.3 (2C), 136.0, 141.6, 197.5. Anal. Calcd for C17H16OSe:
C, 64.76; H, 5.12. Found: C, 64.78; H, 5.11.
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2-Iodo cinnamyl(phenyl)selenide (Table 2, entry 6)
Pale yellow liquid; IR (neat) nmax/cm-1 3053, 2924, 1579, 1475,
1
1460, 1433, 1178, 1070, 1008, 956, 734, 688, 655 cm-1; H NMR
(CDCl3, 500 MHz) d 3.70 (d, J = 7.5 Hz, 2H), 6.15–6.22 (m, 1H),
6.47 (d, J = 15.5 Hz, 1H), 6.85–6.88 (m, 1H), 7.21–7.27 (m, 4H),
7.36–7.38 (m, 1H), 7.53–7.55 (m, 2H), 7.77 (d, J = 8 Hz, 1H); 13
C
NMR (CDCl3, 125 MHz) d 30.2, 99.7, 126.6, 127.4, 128.3, 128.9,
129.1 (2C), 129.2, 129.6, 133.8 (2C), 135.5, 139.4, 139.9. Anal.
Calcd for C15H13ISe: C, 45.14; H, 3.28. Found: C, 45.16; H, 3.29.
Acknowledgements
We are pleased to acknowledge the financial support from DST,
New Delhi through J. C. Bose Fellowship [Grant No. SR/S2/JCB-
24 U. Bremberg, S. Lutsenko, N.-F. Kaiser, M. Larhed, A. Hallberg and
C. Moberg, Synthesis, 2000, 1004.
This journal is
The Royal Society of Chemistry 2011
Org. Biomol. Chem., 2011, 9, 1763–1767 | 1767
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