Direct carboxylation of allylic halides with carbon dioxide in the presence of indium

Article abstract of DOI:10.1039/c4cc00148f

A highly regioselective indium-mediated allylation of carbon dioxide starting from simple allylic halides (X = I, Br, Cl) has been developed. No transition metal catalyst is needed and an inert atmosphere is not necessary. The reaction tolerates a wide range of synthetically attractive functional groups with a very high branched regioselectivity. The Royal Society of Chemistry 2014.

Full text of DOI:10.1039/c4cc00148f

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Direct carboxylation of allylic halides with
carbon dioxide in the presence of indium†
Bukeyan Miaoa and Shengming Ma*ab
Cite this: Chem. Commun., 2014,
50, 3285
Received 8th January 2014,
Accepted 29th January 2014
DOI: 10.1039/c4cc00148f
www.rsc.org/chemcomm
A highly regioselective indium-mediated allylation of carbon dioxide
starting from simple allylic halides (X = I, Br, Cl) has been developed.
No transition metal catalyst is needed and an inert atmosphere
is not necessary. The reaction tolerates a wide range of synthe-
tically attractive functional groups with a very high branched
regioselectivity.
The activation of carbon dioxide has been a hot topic, which
boasts great potential in the field of energy and environmental
protection Moreover, CO2 excels in carbon–carbon bond for-
mation reactions as a nontoxic, abundant and inexpensive, yet
highly inactive C1 starting material, especially in the synthesis
of carboxylic acids.1 Thus, smooth transformations using cheap
and easily acquired reagents such as arenes,2 alkenes,3 allenes,4
alkynes,5 aryl halides6 and benzyl halides7 have drawn wide-
spread attention.
Scheme 1 Previous work and our concept of the allylation of CO2.
Although the catalyzed carboxylation of aryl halides Thus, the direct carboxylation of allyl halides in the presence
mediated by a stoichiometric amount of metal has been well of a metal which display wide functional group tolerance is
established,6 similar transformation in allyl halides is surpris- surely the best choice for the synthesis of 3-alkenoic acids.
ingly unsettled.7 Traditional reactions of allyl lithium or Thus, identifying a metal for the direct transformation of allylic
Grignard reagents with CO2 seriously suffer from the substrate halides to 3-alkenoic acids with a practical regioselectivity
scope for the functionality group tolerance due to the high referring the position of CQC bonds in the products as well
reactivity of these allylmetal reagents.8 On the other hand, as branched vs. linear selectivity is highly desired (Scheme 1).
transition metal-catalyzed carboxylation reactions starting from With great advantages including its nontoxic nature, wide
preformed allylmetals including allylstannanes and allyl- functional group tolerance and friendly operation, allylindium
boranes encounter the problem of toxicity and sometimes species has shown its potential in the allylation in the last few
affording a mixture of 2- and 3-alkenoic acids.9–12 To solve decades.13 Although the allylation of aldehydes and ketones
this problem, in most cases, highly electron-rich ligands were well established, the related allylation of CO2 mediated by
such as pincer-type diphosphine and NHC are necessary. indium has never been reported. Herein, we report the realiza-
tion of our concept using indium.
After trying some metals with common solvents, we observed
that when allyl bromide was treated with 0.67 equiv. of indium
powder14 in DMF at 60 1C with a CO2 balloon, the expected
product 2a was afforded albeit in only 14% yield. Rescreening
in other solvents did not give better results. After some
trials, we found that pressure plays a critical role in the
reaction: the yield sharply increased upon raising the
pressure of CO2 and reached the peak (68%) with 2 MPa of
a Shanghai Key Laboratory of Green Chemistry and Chemical Process,
Department of Chemistry, East China Normal University, 3663 North Zhongshan Lu,
Shanghai 200062, P.R. China. E-mail: masm@sioc.ac.cn; Fax: +86-21-6260-9305
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu,
Shanghai 200032, P.R. China
† Electronic supplementary information (ESI) available: Experimental proce-
dures, characterization data, and copies of 1H NMR and 13C NMR spectra. See
DOI: 10.1039/c4cc00148f
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Table 3 The scope of In-mediated allylation of carbon dioxidea
CO2 (Table 1, entry 5, for the effect of pressure on the reaction,
see Scheme S1, ESI†). It should be pointed out that such a
pressure is easy to achieve in the laboratory and industrial
processes.
The yield dropped to 32% at 45 1C and 6% at rt (19 1C)
(Table 1, entries 7 and 8). Increasing the ratio of In:allyl Entry
R
Yield of 2b
bromide did not improve the yield (Table 1, entries 9 and 10).
1
Ph
69 (2b)
Interestingly, when 1.0 equiv. of CsF5l,o,15 was added, the
yield with allyl bromide was further improved to 72% (Table 1,
entry 11).
2
3
4
5
1-Naphthyl
Bn
63 (46c) (2c)
72 (2d)
p-tol
58 (2e)
nC6H13
62d (40c) (2f)
a
The reaction was conducted with 1.5 mmol of 1, 1.0 mmol of In
Table 1 Optimization of the reaction conditionsa,b
(powder, 425 mesh) and 1.5 mmol of CsF under a 2 MPa CO2 atmosphere
in 5 mL of anhydrous DMF at 60 1C. Isolated yield. The reaction was
conducted in the absence of CsF. The reaction was conducted using
b
c
d
1.2 mmol of 1c.
Entry Solvent CO2 (MPa) Temp. (1C) Ratio In : S.M. Yield of 2ac
The carboxylation reaction of several commercially available
allylic bromides was also attempted, which was followed by
esterification to afford the benzyl ester 3g–j. In addition to
2-methylallyl bromide [Scheme 2, eqn (1)], 3-bromocyclohexene
may also undergo the reaction to afford the corresponding ester
3h in 61% yield [Scheme 2, eqn (2)]. Importantly, the carboxyl-
ation of crotyl bromide afforded the branched product 3i
specifically with no linear regioisomer formed as judged by
1H NMR analysis of the crude mixture [Scheme 2, eqn (3)]. An
all-carbon quaternary center was also formed via such a trans-
formation by using 3-methyl-2-butenyl bromide affording 3j
[Scheme 2, eqn (4)].
1
2
3
4
5
6
7
8
DMF
DMF
THF
0.1
3.0
3.0
3.0
2.0
0.5
2.0
2.0
2.0
2.0
2.0
2.0
60
60
60
60
60
60
45
r.t. (19)
60
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.5
1 : 1.3
1 : 1.1
1 : 1.5
1 : 1.5
14
59
23
39
68
44
32
6
69
65
72d
61e
DMI
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
9
10
11
12
60
60
60
a
The reaction was conducted with 1.5 mmol of allylic halide and In
b
(powder, 425 mesh) under CO2 in 5 mL of an anhydrous solvent. For a
c
complete list of optimization of reaction conditions, see ESI. Determined
by 1H NMR analysis using CH2Br2 as the internal standard. 1.0 equiv. of
d
e
CsF was added. 1.0 equiv. of LiCl was added.
It is worth noting that allyl chloride may also react upon
addition of 1.0 equiv. of LiI although the yield is a little
bit lower as compared with allyl bromide (Table 2, entry 2);
allyl iodide afforded the adduct in 54% yield (Table 2,
entry 3).
Table 2 Survey of other halidesa
Entry
X
Additive
Yield of 2ab
Scheme 2 Reaction of commercially available allylic bromides.
1
2
3
Cl
Cl
I
—
n.d.
55
54
LiI (1.0 equiv.)
—
Substrates with p-F, p-Cl and p-CF3-substituents may be
applied (Table 4, entries 1–3). Furthermore, functional groups
such as ester and cyano group may be well tolerated (Table 4,
entries 4 and 5). Although the acetyl group is not compatible,
the ketal functionality survived the carboxylation affording
a
The reaction was conducted with 1.5 mmol of allylic halide and
1.0 mmol of In (powder, 425 mesh) under a 2 MPa CO2 atmosphere
in 5 mL of anhydrous DMF at 60 1C. Determined by 1H NMR analysis
using CH2Br2 as the internal standard.
b
The substrate scope of the reaction has been explored under 2p in good yield (Table 4, entry 6). The reaction of propargyl
the optimal conditions (Table 1, entry 11). The reaction pro- bromide under the same conditions led to a complicated
ceeds with both 2-aryl, -benzyl, and -alkyl-substituted allylic mixture.
bromides (Table 3, entries 1–5). In addition to 2b, the reaction
The same product was obtained from both 2-butenyl and
of 2-phenylallyl bromide also afforded 2-phenylpropene (9%) 3-buten-2-yl chlorides, indicating the common delocalized allylic
and a trace amount of 2,5-diphenyl-1,6-hexadiene.
intermediate for such a transformation (Scheme 3).
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Entry
R
Yield of 2b
1
2
3
4
5
p-F
p-Cl
p-CF3
p-COOEt
m-CN
76 (2k)
70 (2l)
61 (2m)
70 (31c) (2n)
50 (2o)
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Lett., 2013, 15, 977.
6
58 (2p)
a
The reaction was conducted with 1.5 mmol of 1, 1.0 mmol of In
(powder, 425 mesh), 1.5 mmol of CsF under a 2 MPa CO2 atmosphere in
5 mL of anhydrous DMF at 60 1C. Isolated yield. Without CsF.
b
c
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´
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In conclusion, we have developed a novel and convenient
way to synthesise b,g-unsaturated carboxylic acid directly from
CO2 and allylic halides. No transition metal catalyst is necessary.
The reaction tolerates many synthetically useful functional groups
such as halogen, CF3, ester, cyano, acetal and the same branched
products were specifically obtained when starting from either
a- or g-substituted allylic halides. The pressure effect and addition
of CsF are responsible for this transformation. Further research
on this type of carboxylation reaction is underway in our group.
Financial support from the National Basic Research Program
of China (2011-CB808700), National Natural Science Foundation
of China (21232006) and Shanghai Municipal Committee of
Science and Technology (12JC1-403700) is greatly appreciated.
We thank Tao Cao in this group for reproducing the results of
entry 4 in Table 3, eqn (4) in Scheme 2 and entry 4 in Table 4.
´
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14 Allylindium sesquihalide is generally considered as the allylindium
species formed in DMF or THF. See, S. Araki, H. Ito and Y. Butsugan,
J. Org. Chem., 1988, 53, 1831. In this study, we have quenched the
following reaction with DOAc, which also indicates the formation of
an allylic indium intermediate.
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