2,2-Diiododimedone: A mild electrophilic iodinating agent for the selective synthesis of α-iodoketones from allylic alcohols

Article abstract of DOI:10.1039/c7cc04823h

2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a new electrophilic iodinating agent that selectively iodinates electron-rich aromatics. In contrast to other common electrophilic iodinating reagents, its mild nature allows it to be used for the selective synthesis of α-iodinated carbonyl compounds from allylic alcohols through a 1,3-hydrogen shift/iodination process catalyzed by iridium(iii) complexes.

Full text of DOI:10.1039/c7cc04823h

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DOI: 10.1039/C7CC04823H
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Received 00th January 20xx,
2,2-Diiododimedone: a mild electrophilic iodinating agent for the
selective synthesis of α-iodoketones from allylic alcohols
Samuel Martinez-Erro,† Antonio Bermejo Gómez,† Ana Vázquez-Romero, Elis Erbing, and Belén
Martín-Matute*
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a chemo- or regioselectivity. Thus, the development of mild and
new electrophilic iodinating agent that selectively iodinates selective electrophilic iodination methods remains
electron-rich aromatics. In contrast to other common electrophilic challenging and desirable goal for synthetic chemists.
a
iodinating reagents, its mild nature allows it to be used for the
We have previously reported the use of iridium catalysts for
selective synthesis of α-iodinated carbonyl compounds from allylic the conversion of allylic alcohols (1) into α-functionalized
alcohols through a 1,3-hydrogen shift / iodination process carbonyl compounds.11,7c,8c,12 Carbon and halogen (i.e., F, Cl,
catalyzed by iridium(III) complexes.
and Br) functional groups could be introduced through a
process involving a 1,3-hydrogen shift mediated by the metal
complex. This process allows the selective formation of either
the α or α’ constitutional isomer, as the new bond is
constructed exclusively at the carbon that was originally part
of the olefin. Attempts to introduce an iodide failed in our
hands, mainly due to the high reactivity of the available
electrophilic iodinating agents, but also due to the instability of
the starting allylic alcohols and/or the final iodoketones under
the reaction conditions. In this paper, we report the
development of a new mild iodinating agent (Scheme 1, top)
and its application in electrophilic iodination of aromatic
compounds, and also in the synthesis of α-iodoketones (3)
from allylic alcohols mediated by iridium catalysts (Scheme 1,
bottom). This methodology allows for the first time the one-
step synthesis of α-iodoketones as single constitutional
isomers from allylic alcohols in a one-step procedure. The
utility of α-iodoketones for the preparation of valuable
Halogenated organic compounds are ubiquitous, not only as
natural products,1 but also as synthetic compounds, and they
have applications in medicinal chemistry,2 agrochemistry,3 and
materials science.4 The halogen functional group is very
versatile. It can participate in many synthetic transformations,
including
nucleophilic
substitutions,
eliminations,
dehydrohalogenations, and oxidative additions to metal
centers. The nature of the halogen gives each carbon–halogen
bond unique properties,5 resulting in numerous applications in
synthetic organic chemistry.
Significant progress has been made in the development of
synthetic methods for the construction of C−F bonds, by both
electrophilic and nucleophilic approaches.6 There also exist
many synthetic methods for the nucleophilic and electrophilic
chlorination7 and bromination8 of organic molecules. When it
comes to electrophilic methods for the construction of C−I
bonds reagents such as I2, NIS (N-iodosuccinimide), IPy2BF4
(Barluenga´s reagent), and ICl have been widely used in
organic synthesis.9 Also, methods based on the conversion of
iodide into the corresponding iodonium species through
oxidation have also been reported.10 These methods have
some drawbacks, however, such as the high reactivity of the
electrophilic iodinating agents, or the need for strong oxidizing
agents, which result in low functional-group tolerance and low
I
I
O
O
O
O
Gram scale
ICl
Stable solid
1,4-dioxane
RT, 6 h
Purification by filtration
2 (75%)
O
OH
[Cp*Ir]cat
R
O
R
R1
R1
α
α’
α’
α
Department of Organic Chemistry, Arrhenius Laboratory,
Stockholm University, 10691 Stockholm, Sweden.
E-mail: belen.martin.matute@su.se
I
I
3
1
I
O
† These authors contribute equally to this work.
2
Electronic Supplementary Information (ESI) available: detailed synthetic
procedures, characterization, NMR spectra, optimization tables and deuterium
labelling studies. See DOI: 10.1039/x0xx00000x
Scheme 1 Synthesis of 2,2-diiododimedone (2, top) and of α-iodocarbonyl
compounds from allylic alcohols.
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Table 1 Optimization.a
building blocks is also presented.
View Article Online
DOI: 10.1039/C7CC04823H
[Cp*Ir]cat
2 (1.2 equiv.)
Solvent
OH
O
O
The synthesis of the new iodinating reagent, 2,2-
diiododimedone (2), was easily accomplished by treatment of
dimedone with iodine monochloride in 1,4-dioxane at room
temperature. The synthesis of 2 can be carried out on a gram
scale, and purification by simple filtration gives the product in
excellent yield. We initially tested 2 as an iodinating agent for
aromatic compounds (Scheme 2). In optimization studies, the
best results were obtained using a catalytic amount of FeCl3,
and hexafluoroisopropanol (HFIP) as the solvent. The need to
use these conditions reflects the mildness of 2, which is
important for increasing the functional group tolerance in
electrophilic halogenation reactions. After a short optimization
(see ESI), we found that anisole 4a could be iodinated under an
air atmosphere in just 2 h. Two other substrates were also
iodinated using these reaction conditions; both N,N-
dimethylaniline (4b) and N-pivaloyl indole (4c) were converted
into the corresponding iodinated analogues (5b and 5c) in very
good yields after short reaction times and with excellent
regioselectivity.
+
C5H11
C5H11
3a
C5H11
1a
6a
I
RT, 16 h
[Cp*IrCl2]2
[Cp*Ir(H2O)3]SO4
[(Cp*Ir)2(OH)3]OHŸ11H2O
I
II
III
Entry
Catalyst
Solvent (v / v)
Conv.
[%]b
>99
86
3a/6a [%]b,c
1
2
I
I
Acetone/H2O (1:1)
THF/H2O (1:1)
36/64
58/28
85/11
93/6
92/8
91/9
90/10
93/5
94/6
79/7
88/4
3
I
2-MeTHF/H2O (1:1)
2-MeTHF/H2O (1:1)
2-MeTHF/H2O (1:1)
2-MeTHF/H2O (1:2)
2-MeTHF/H2O (1:2)
2-MeTHF/H2O (2:1)
2-MeTHF/H2O (2:1)
2-MeTHF/H2O (2:1)
2-MeTHF/H2O (2:1)
96
99
4
5
6
7
8
9
II
III
II
III
II
III
II
III
>99
>99
>99
98
>99
86
10d
11d
92
a
b
Unless otherwise noted: 1a (0.5 mmol, 0.1 M) and 2 mol% of [Ir] was used.
Determined by 1H NMR spectroscopy. Octan-3-one was not formed. 1 mol%
c
d
of [Ir].
I
I
Table 2 Evaluation of a variety of iodinating agents.a
O
O
FeCl3 H2O (10 mol%)
HFIP, RT, 2 h
Ar
H
+
Ar
5a-5c
I
[Cp*Ir]cat (III, 1 mol%)
4a-4c
Iodinating agent
2
OH
O
O
(1.2 equiv.)
I
+
C5H11
I
I
C5H11
C5H11
3a
Solvent
1a
6a
I
RT, 16 h
N
O
MeO
Me2N
5a
82%
5b
68%
5c
81%
tBu
Entry
Reagent
Conv. [%]b
3a/6a [%]b
1
2
3
4
5
6
7
8
9
2
I2
ICl
>99
66
66
>99
>99
<5
4
25
95
90
76
94/6
-/3c
-/1c
17/-
-/-
Scheme 2 Iodination of electron-rich aromatics using 2.
NIS
IPy2BF4
-
Next, we evaluated the performance of 2 in the iridium-
catalyzed isomerization / α-iodination of allylic alcohols. For a
successful outcome, the reaction must take place under mild
conditions, and the starting alcohols (1) and final products (3)
should not undergo undesired iodination. Oct-1-en-3-ol (1a)
was chosen as a model substrate for the optimization studies,
and several Ir(III) catalysts and solvents were evaluated (Table
1). When [Cp*IrCl2]2 (I, 2 mol% [Ir]) was used as the catalyst in
a mixture of acetone and H2O (1:1), full conversion was
observed, but only 34% of the desired product 3a was formed,
together with 64% of α,β-unsaturated ketone 6a (entry 1). This
solvent mixture gave, on the contrary, excellent results in the
bromination of allylic alcohols.8c The use of THF / H2O (1:1)
resulted in a clear decrease in the formation of 6a (entry 2).
This effect was even clearer when THF was replaced by 2-
methyltetrahydrofuran (2-MeTHF). In this case, the desired α-
iodinated compound (3a) was obtained in 85% yield and only
11% of 6a was formed (entry 3). The amount of 6a could be
decreased further by using [Cp*Ir(H2O)3]SO4 (II) or
-
-
2d
d
e
I2
-
-
-
-
ICld
e
e
10
11
NISd
d
e
IPy2BF4
Unless otherwise noted: 1a (0.5 mmol, 0.1 M). Determined by 1H NMR
a
b
c
d
spectroscopy 28% (entry 2) and 21% (entry 3) of octan-3-one was formed.
Without [Ir] catalyst. e A mixture of unknown by-products was observed.
and 9), while a very good yield for 3a was maintained.
Increasing the proportion of 2-MeTHF further did not prevent
the formation of 6a, and also compromised the conversion
(See ESI for a full description of solvent effects). When the
catalyst loading was decreased to 1 mol% [Ir], catalyst III was
better than II (entries 10 and 11). When 0.6 and 0.2 equiv. of 2
were used, yields of 70 and 27%, respectively, were observed
(see ESI). This result suggests that more than one iodo unit can
be donated by the reagent. All reactions were carried out
under an atmosphere of air.
[(Cp*Ir)2(OH)3]OHŸ11H2O (III) as catalysts (entries 4 and 5).
When the proportion of H2O in the solvent mixture was
increased (i.e., 1:2), higher amounts of the undesired 6a were
formed (entries 6 and 7); when the proportion of 2-MeTHF
was increased, the yield of 6a dropped to just 5-6% (entries 8
2 | Chem. Commun., 2017, 00, 1-3
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When compared to other electrophilic iodinating reagents, give α-amino ketones as single constitutional isomers (Scheme
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DOI: 10.1039/C7CC04823H
the superiority of 2 was clearly seen (Table 2). None of the 4).
other reagents tested were able to give good yields of 3a,
mainly due to decomposition of the starting allylic alcohol 1a
(entries 1-5). This is not surprising, since it is well known that
double bonds promptly react with these reagents to give cyclic
iodonium ions. This undesired reaction was not observed
when 2,2-diiododimedone (2) was used. A series of control
experiments was also carried out (Table 2, entries 6-11).
Catalyst III was not able alone to react with the allylic alcohol
in the absence of 2 (entry 6). We recently reported that the
presence of a halogen ligand on Ir is important for the activity
of [Cp*Ir] complexes of this type, and described the in situ
formation of such an Ir−halogen bond through reaction of the
Ir precatalyst with the halogenating agent.13 In another control
experiment, we observed that 2 does not react with allylic
alcohol 1a in the absence of the iridium catalyst after 16 h
(entry 7). It can therefore be concluded that the mildness of
iodinating agent 2 is key to the success of this tandem
In conclusion, we present a new mild and selective
Table 3 Substrate scope.a
OH
O
III (1 mol%)
2 (1.2 equiv.)
R1
R2
R1
3a-3r
R2
2-MeTHF / H2O
(2:1)
1a-1r
I
RT, 16 h
O
O
O
O
Bu
BnO
C5H11
Cy
I
Et
I
I
I
3d
3a
3b
3c
96% (78%)
83% (68%)
86% (74%)
56% (48%)
O
O
O
Ph
Ph
I
I
I
3f
3g
3e
81% (67%)
78% (66%)
47% (34%)
O
O
O
Ph
Ph
I
I
I
3i
3j
3h
isomerization
/
halogenation reaction. Mechanistic
Cl
Br
68% (55%)
78% (66%)
70% (55%)
investigations were carried out with deuterium-labelled
alcohols, and the results suggest that an intramolecular 1,3-H
shift is operating under these reaction conditions (see ESI).
Having established these optimized reaction conditions, we
went on to study the scope of the reaction (Table 3). Alcohols
1a-1f and 1k-1m bearing a terminal double bond gave the
corresponding α-iodocarbonyl compounds (3a-3f and 3k-3m)
in high yields within 16 h. Allylic alcohols with internal double
bonds (1g-1j) were also converted into the corresponding α-
iodinated products in good yields. Additional double bonds in
the molecule were unaffected (1f and 1g); only the allylic
alcohol functionality reacted. The reaction is not restricted to
secondary alcohols; primary alcohols gave the corresponding
α-iodoaldehydes (3n-3r) in moderate to good yields. The
stability of the products during the purification process
accounts for the difference between the yields estimated
against an internal standard and the isolated yields.
O
O
O
Ph
I
I
I
3l
3m
70% (55%)
3k
iBu
87% (72%)
89% (74%)
O
O
O
H
Ph
H
H
3o
3p
I
61% (34%)
I
I
3n
Cl
87% (21%)
58% (37%)
O
O
BnO
Ph
H
H
3r
38% (23%)
3q
51% (42%)
I
I
1
aReactions carried out on a 1 mmol scale (0.1 M). Yield determined by H NMR
spectroscopy. Isolated yields in parentheses.
O
OH
NaBH4
Ph
Ph
MeOH, -60 oC, 30 min
3e
8
I
I
The utility of α-iodoketones as versatile intermediates for
59% from 1e (97:3 d.r.)
organic synthesis was demonstrated in
a
series of
KCN
K2CO3
MeCN
reflux
o.n.
NH
THF, 40 o
o.n.
C
tBuOK
HCl
THF, 0 o
30 min
C
transformations (Schemes 3 and 4). First, the synthesis of
imidazole 7 was easily accomplished by allowing an amidine to
react with α-iodoketone 3e. In a one-pot procedure starting
from 1e, iodohydrin 8 was synthesized in 59% yield with
excellent diastereoselectivity (93:7). Subsequent basic
treatment gave the corresponding epoxide 9 with excellent
diastereoselectivity. α-Cyanoepoxide 10 was also prepared in
good yield and with a good diastereomeric ratio in one step by
the reaction of 3e with KCN.
Ph
NH2
Ph
NC
O
O
N
Ph
Ph
HN
7
95%
10
9
Ph
74% (80:20 d.r.)
70% (97:3 d.r.)
Scheme 3 α-Iodoketones as versatile synthetic intermediates.
The synthetic utility of α-iodocarbonyl compounds was also electrophilic iodinating reagent, 2,2-diiododimedone (2). Using
demonstrated by the preparation of valuable α-aminoketones. this reagent, we have been able to carry out the first selective
This structural motif is found in many compounds with synthesis of α-iodocarbonyl compounds as single
important biological activities.14 Although there are several constitutional isomers. The method relies on an iridium-
procedures for the synthesis of compounds containing this catalyzed 1,3-hydrogen shift mediated by iridium(III)
motif, their regioselective preparation when two enolizable complexes. The utility of α-iodocarbonyl compounds has been
positions are present remains a challenge.14b-d We found that demonstrated by their conversion into other important
secondary amines react with α-iodocarbonyl derivatives — organic structures for which selective synthetic procedures
prepared from allylic alcohols as described in this paper — to have not previously been available.
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Yang, Y. Wang, X.-S. Xue and J.-P. CheDnOg,I:J1.0O.10rg3.9/CCh7eCmC0. 42802137H,
82, 4129.
O
O
R3R4NH (3 equiv.)
R1
R2
R1
R2
11-15
7
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1,4-Dioxane
RT, 16 h
I
3e or 3h
N
R3
R4
O
O
O
Ph
Ph
Ph
11
89%
12
51%
13
73%
N
N
N
N
O
O
N
N
Ph
14
77%
Ph
N
15
88%
N
S
8
9
Scheme 4 Regioselective synthesis of α-amino ketones.
Acknowledgements
This project was supported by the Swedish Research Council
(VR), the Swedish Research Council Formas, and the Knut and
Alice Wallenberg Foundation. We also thank the Swedish
Governmental Agency for Innovation Systems (VINNOVA) for a
VINNMER grant to B.M.-M.
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OH
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ChemComm
R1
R2
R1, R2 = alkyl, aryl, H
I
I
O
O
[Cp*Ir]cat
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New iodinating agent
Easy synthesis at gram-scale
Mild and high functional group tolerance
O
R1
R2
I
18 examples
Versatile building blocks