Iodoarene-catalyzed oxidative transformations using molecular oxygen

Article abstract of DOI:10.1039/c7cc05160c

Molecular oxygen serves as a useful oxidant for the glycol scission of 1,2-diols and the Hofmann rearrangement of primary amides using pentamethyliodobenzene as a catalyst. The use of isobutyraldehyde and Lewis basic nitriles under O₂ enabled the iodine(i)/(iii) catalytic cycle, where in situ-generated peracid acts as a terminal oxidant.

Full text of DOI:10.1039/c7cc05160c

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
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Iodoarene-catalyzed Oxidative Transformations Using Molecular
Oxygen
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a
b
a
a
a
a
K. Miyamoto,* J. Yamashita, S. Narita, Y. Sakai. K. Hirano, T. Saito, C. Wang, M. Ochiai, and
M. Uchiyama*
a,c
DOI: 10.1039/x0xx00000x
www.rsc.org/
4
Molecular oxygen serves as a useful oxidant for glycol scission of oxidants have greatly enhanced their synthetic utility. We
1
,2-diols and Hofmann rearrangement of primary amides using have also reported iodobenzene-catalyzed oxidative
5
pentamethyliodobenzene as a catalyst. Use of isobutyraldehyde transformations, including α-acetoxylation of ketones,
6
and Lewis basic nitriles under O enabled iodine(I)/(III) catalytic oxidative cleavage of carbon–carbon multiple bonds, and
2
7
cycle, where in situ-generated peracid acts as a terminal oxidant.
Hofmann rearrangement of primary carboxamides. However,
these methods generally need notoriously explosive peracids,
1
g-i,8,9
such as peracetic acid or m-CPBA.
Several alternative
®
Introduction
terminal oxidants have also been reported. 1) Oxone was
developed as a safer terminal oxidant, but its use was
essentially limited to aqueous media because of poor solubility
Hypervalent iodine compounds have been widely used in
3
organic synthesis. Aryl-λ -iodanes with two heteroatom ligands
1
g-i,8,10,11
in organic solvents.
2) Positive halogen sources such as
(ArI(X)Y) now occupy a privileged position in oxidative
®
N-bromosuccinimide (NBS) and Selectfluor were reported as
transformations for organic synthesis because of their excellent
oxidizing ability towards a wide range of organic compounds,
1
low toxicity, and stability to heat and moisture. For example,
4
d,4i,4m,4n
fungible oxidants,
restricted by their high cost (NBS: 23$/mol; Selectfluor :
but their synthetic utility is
®
1
35$/mol). Therefore, replacement of them with molecular
2
9
oxidative cleavage of 1,2-diols (glycol scission) and Hofmann
rearrangement of primary amides proceed cleanly under mild
1
O2 is an attractive solution. We report herein the first
3
example of O -mediated oxidative transformations (glycol
2
conditions, providing
synthetically complex organic molecules. Nicolaou and co-
workers have elegantly demonstrated that
diacetoxyiodo)benzene ( ) enables highly chemoselective
glycol scission of 1,2-diols while leaving a wide range of
a
unique and valuable entry to
2
,3
scission and Hofmann rearrangement) under mild reaction
conditions,
in
which
isobutyraldehyde
and
pentamethyliodobenzene act as O -mediator and catalyst,
2
(
1
respectively.
2
a
functionalities intact (Scheme 1). Fukuyama et al. have
successfully established a late-stage Hofmann rearrangement
by using
1 as a key step leading to total syntheses of (–)-
3
i,j
oxycodone and (–)-oseltamivir.
However, from the
viewpoints of reagent cost and by-products formation, use of
3
catalytic amount of ArI(X)Y-type λ -iodane would be
preferable, but this is not yet well established.
Recent developments in simple methodologies for in situ
3
generation of λ -iodanes with commercially available terminal
Scheme 1. Recent sophisticated examples of oxidative transformations using
2
stoichiometric amount of PhI(OAc) .
Results and discussion
Aldehyde is gradually oxidized to carboxylic acid by
1
4,15
molecular O through peracid
2
4
(Scheme 2a).
It occurred to
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us that the in situ-generated peracid would be a suitable 12–16). This is attractive from a synthetic viewpoint, because
1
2,19
oxidant for iodoarene catalysis if undesired consumption of 6a is an inexpensive petroleum-derived aldehyde (3$/mol).
1
6
peracid via Criegee intermediate
5
was suppressed. We Note that the reaction proceeds smoothly even in air or in the
thought that the key to control the formation of peracid might dark (entries 17 and 18). Importantly, the in situ-generated
be the use of sterically hindered aldehyde. In our initial study, peracid is a transient species and could not be detected at all at
the autoxidation of isobutyraldehyde (6a) under an O
2
the end of the reaction, enabling the reaction to be safely
2
atmosphere (1 atm) in 1,2-dichloroethane (DCE) at 40 °C was scaled-up (entry 19). Gratifyingly, the amount of 6a can be
0
quite fast, and after only 1 h perisobutyric acid was formed as reduced to 1.5 eq on 10 mmol scale (entry 20).
a
prominent species (Fig. S1). Further reaction with
a
Table 1 Catalytic oxidative cleavage of 1,2-diol 7a
iodobenzene (8a) proceeded at a reasonable rate to afford a
mixture of hypervalent iodine(III) species in high yield (5 h,
75%). Encouraged by these results, we applied this approach to
the oxidative cleavage of 1,2-diols (Table 1).
(
a)
O
O
O
O
O
Entry
solvent
DCE
Ar–I 8
R–CHO 6
time
(h)
25
9
yield
O
2
+
O O
b
R
R
H
R
O
(
mol%) (R = )
(%)
(or In•)
HOO•
O
1
2
3
4
5
6
7
8
9
8a (10) 6a (i-Pr)
8a (10) 6a (i-Pr)
8a (10) 6a (i-Pr)
8a (10) 6a (i-Pr)
8a (10) 6a (i-Pr)
8b (10) 6a (i-Pr)
45
43
0
R
H
O
R
H
CHCl
PhH
3
O
3
O
O
R
OH
4
11
7
R
O
OH
CyH
0
O
O
+
R
O
O
R
R
OH
R
OH
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
48
72
24
11
10
24
24
48
32
24
24
99
43
100
100
100
100
9
H
5
(b)
Autoxidation
O
8c (10)
6a (i-Pr)
O
2
R = Electron
donating group
OO
8d (10) 6a (i-Pr)
O
O
O
R
I
OH
8e (10)
8e (5)
–
6a (i-Pr)
6a (i-Pr)
6a (i-Pr)
6b (Me)
6c (n-pent)
6d (t-Bu)
6e (Ph)
:
Bulky
substituent
1
0
O
OH
O
11
12
13
I
O
OOH
R'
R'
R'
NH2
8e (5)
8e (5)
8e (5)
8e (5)
8e (5)
8e (5)
8e (5)
8e (5)
8e (5)
66
95
H
OH
O
H
R
N
R'
OH R'
Oxidative
transformation
CO Me
c
ArI–ArI(III) cycle
2
1
1
1
1
1
4
5
6
7
8
86
c
92
Scheme 2. (a) Mechanism of autoxidation of aldehyde. (b) Working hypothesis.
c
6e (3-ClC
6a (i-Pr)
6a (i-Pr)
6a (i-Pr)
6a (i-Pr)
6
H
4
) 24
54
d
e
24
24
48
48
100
In the presence of 10 mol% of 8a and 3 eq of 6a, exposure of
90
1
,2-diol 7a to molecular O (1 atm) in DCE at 40 °C resulted in
2
glycol scission to give acetophenone (9a) in 45% yield (entry 1). 19f
This is the first example of iodoarene-catalyzed O -mediated
90 (74)
77 (68)
2
f,g
2
0
glycol scission. Use of other non-polar solvents did not improve
the yield of 9a (entries 2–4), but afforded significant amounts
of Baeyer-Villiger oxidation (BVO) product, isopropyl formate
a
b
2
Conditions: 7a (0.24 mmol, 0.2 M)/6 (3 eq)/O (1 atm). GC yields. Isolated yield
c 1
d
e
f
is given in parentheses. H NMR yields. In the dark. In air. 7a (10 mmol) was
g
used. 6a (1.5 eq) was used.
1
6
and isobutyric acid. In contrast, acetonitrile (possessing a
1
greater hydrogen bond acceptor basicity, β value = 0.40)
7
With these optimized conditions in hand, we studied the scope
of the new protocol, which proved effective for the glycol
scisson of a wide range of 1,2-diols (Table 2). Dihydrobenzoin
1
8
dramatically improved the yield of 9a (entry 5). In this
system, electron-rich iodoarenes showed excellent catalytic
activity, probably due to a greatly enhanced rate of formation
of iodine(III) species, as well as suppression of over-oxidation
of 9a (e.g., α-hydroxylation, BVO, and so on) (entries 6–8).
However, highly electron-rich 2,4,6-(trimethoxy)iodobenzene
(
7b) was cleanly converted to benzoic acid (9b) in 76% yield
after Pinnick oxidative workup. The electronic effect at benzylic
carbons had little influence on the reactivity of diols and
various dihydrobenzoins with an electron-donating group (p-
and aliphatic iodobutane, resulted in a decreased yield of 9a
7
MeO or Me) or an electron-withdrawing group (Cl or CF ) on
3
(
30-33%), probably because of degradation of the catalyst.
the phenyl ring were also smoothly cleaved to give the
Among various iodoarenes, pentamethyliodobenzene (8e) was
the best (entry 9). Although both aliphatic and aromatic
aldehydes can be used, best result was obtained by 6a (entries
corresponding carboxylic acids 9c-f within 24 h in good yields.
In addition, various mono- and di-substituted diols 7g-j were
2
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compatible with the reaction conditions. Sterically congested cannot survive. In addition, 2) aromatic amides cannot be
2
3
tri- and tetra-substituted diols 7k
reaction. It is interesting to note that typical oxidants for glycol overcomes these drawbacks. Exposure of benzamide (11a) to
scissions, such as NaIO , generally cannot cleave cyclic trans- 8e (10 mol%) and 6a (3 eq) under O resulted in the generation
-n were not deleterious to the used, because of over-oxidation. The present system using O
2
4
2
diols with a large and rigidly held distance between two oxygen of the corresponding isocyanate 12a, which was trapped by
atoms, whereas our methods were also effective for such methanol to give methyl N-phenylcarbamate (13a) in 74% yield
2
e
substrates (7k and 7l). It should be noted that under the (Table 3). Remarkably, the reaction could be reproduced in air
optimized conditions (method A, Table 1, entry 10), the use of without significant decrease in yield (13a: 70%). A variety of
1,2-diols possessing α-C–H bonds caused low reproducibility, amides, including both electron-rich and electron-deficient
probably because of inhibition of autoxidation of 6a. For these benzamides, as well as aliphatic 1°-, 2°-, and 3°-alkyl
cases, a slightly modified reaction conditions (method B) carboxamides, could be utilized. Hofmann rearrangement of
greatly improved the efficiency/reproducibility of the reaction, alkyl- and aryl carboxamide using a stoichiometric amount of
in which pre-mixing of aldehyde 6a and O for 3 h prior to the generally requires a strong base such as KOH in order to
addition of substrate in a less polar solvent system (DCE–t- suppress unwanted side reactions, such as urea formation,
1
2
1
b,3
BuCN (9:1)) was used. The reaction conditions were quite oxidation of the aromatic ring, etc.,
whereas no formation
robust: we found no significant decrease of the yield in air or of any N,N’-dialkylureas or benzoquinone was observed in this
with excess water (10 eq). Interestingly, this system can be system, partly due to the weakly acidic or neutral conditions
4
2
applied to convert 1,3-diketone 10 to 9b, which is not feasible (pH 4-6).
2
1,22
in the absence of iodoarene 8e
.
a
Table 3 Hofmann rearrangement of carboxamide 11.
a,b
2
Table 2 Iodoarene-catalyzed oxidative cleavage of 1,2-diols under O
a
1
b
Isolated yields. H NMR yields are given in parentheses. In air.
Conclusions
2
In summary, we have succeeded in utilizing O as the terminal
oxidant for the first time. This system opens up facile access to
synthetically versatile oxidative cleavage of various 1,2-diols
and Hofmann rearrangement of carboxamides in up to
quantitative yield by reacting the substrate in the presence of 3
eq of i-PrCHO 6a and a catalytic amount of iodoarene 8e under
1
2
atm of O /air at 40 °C. This protocol is applicable to gram-
a
Conditions, diol 7/8e/6a/O
2
(1 atm). Method A: 7 (0.24 mmol)/8e (5 mol%)/6a
scale synthesis and its functional group tolerance compares
favorably with that of previously reported protocols. Studies to
(
3 eq)/MeCN. Method B: 7 (0.1 mmol)/8e (20 mol%)/6a (5 eq)/DCE–t-BuCN (9:1).
b
1
Structures in brackets are starting materials. Isolated yields. H NMR yields are
c
given in parentheses. Isolated yields determined after Pinnick oxidation of the expand the scope of the catalytic oxidative transformations
d
e
f
reaction mixture. In air.
2
H O (10 eq) was added. 6a (5 eq).
and to elucidate the reaction mechanism are ongoing in our
laboratory.
We recently reported the iodoarene-catalyzed Hofmann
rearrangement of carboxamides using m-CPBA as a terminal
7
oxidant. However, this protocol is still unsatisfactory in terms
Acknowledgements
of its rather low functional group compatibility: for example, 1)
This work was supported by JSPS KAKENHI (S) (No. 24229001)
4
strong Brønsted acid, HBF was essential for the smooth
(to M. U.), JSPS KAKENHI (C) (No. 25460016) (to K. M.), and
catalytic reaction, and hence, acid–sensitive functional groups
JSPS KAKENHI (B) (No. 23390006) (to M. O.)
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6
7
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