Iron-catalyzed aerobic oxidation of allylic alcohols: The issue of C=C bond isomerization

Article abstract of DOI:10.1021/ol402434x

An aerobic oxidation of allylic alcohols using Fe(NO₃) ₃·9H₂O/TEMPO/NaCl as catalysts under atmospheric pressure of oxygen at room temperature was developed. This eco-friendly and mild protocol provides a convenient pathway to the synthesis of stereodefined α,β-unsaturated enals or enones with the retention of the C-C double-bond configuration.

Full text of DOI:10.1021/ol402434x

ORGANIC
LETTERS
XXXX
Vol. XX, No. XX
Iron-Catalyzed Aerobic Oxidation of Allylic
Alcohols: The Issue of CdC Bond
Isomerization
000–000
†
Jinxian Liu and Shengming Ma*
,‡
,†,§
Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of
Chemistry, East China Normal University, 3663 North Zhongshan Lu, Shanghai
2
00062, P. R. China, College of Chemistry and Materials Science, Longyan University,
Longyan 364000, P. R. China, and State Key Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu,
Shanghai 200032, P. R. China
masm@sioc.ac.cn
Received July 8, 2013
ABSTRACT
An aerobic oxidation of allylic alcohols using Fe(NO ) 9H O/TEMPO/NaCl as catalysts under atmospheric pressure of oxygen at room
3
3
3
2
temperature was developed. This eco-friendly and mild protocol provides a convenient pathway to the synthesis of stereodefined R,β-unsaturated
enals or enones with the retention of the CÀC double-bond configuration.
9
10
R,β-Unsaturatedaldehydes/ketonesare important inter-
mediates in many organic reactions, such as (hetero)DielsÀ
amount of oxidants such as chromium oxides, MnO ,
2
11
12
DMSO, or hypervalent iodine compounds is needed,
which would produce almost the same amount of waste
and cause serious environmental problems. In addition, the
Z/E-isomerization of R,β-unsaturated carbonyl compounds
was observed during the oxidation of the corresponding
1
2
Alder reactions, Michael addition, (aza) MoritaÀBaylisÀ
3
Hillman reaction, Aldol condensation, Heck coupling,
4
5
6
7
cyclization, etc. There are numerous reports for the
8
synthesis of such compounds. Oxidation of the corre-
13À16
sponding allylic alcohols is the most convenient method
for this transformation. Traditionally, a stoichiometric
allylic alcohols.
(
3) (a) Shi, M.; Liu, X.-G. Org. Lett. 2008, 10, 1043. (b) Bugarin, A.;
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halov ꢁa , S.; Dziedzic,
†
East China Normal University.
Longyan University.
Shanghai Institute of Organic Chemistry.
´
‡
P.; C oꢁ rdova, A.; Vesel ꢁy , J. Adv. Synth. Catal. 2011, 353, 1096. (d) Abaee,
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§
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(
1
0.1021/ol402434x r XXXX American Chemical Society

2
6
On the other hand, molecular oxygen is a natural,
cheap, and eco-friendly oxidant, which was applied in
the oxidation of allylic alcohols as terminal oxidant with
metallic catalyst. It is worth noting that Z/E-isomerization
has also been observed under aerobic oxidation conditions.
For example, Christmann and co-workers have reported a
copper-catalyzed aerobic oxidation/isomerization protocol
of Z-allylic alcohols affording the completely isomerized
products E-R,β-unsaturated aldehydes under mild condi-
1
7
18
19
20
transition-metal catalysts such as Pd, Pt, Au, Ru,
25
2
1
22
23
24
PtÀBi, OsÀCu, V, Cu, Fe, or even without a
2
7
tions in 2012. Therefore, a clean and mild oxidation
method toward allylic alcohols without isomerization is
highly desirable for both academic preparation and indus-
trial scale production. We have focused on the aerobic
oxidation of alcohols and established a general protocol
for the aerobic oxidation of a wide range of alcohols under
mild conditions using Fe(NO ) 9H O/TEMPO/NaCl as
(
6) (a) Jacobsen, C. B.; Jensen, K. L.; Udmark, J.; Jørgensen, K. A.
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(
3
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2
3
catalysts, yielding the corresponding aldehydes or ketones
Organometallics 2012, 31, 6154.
28
in good to excellent yields. Herein, we report our efforts
in the iron-catalyzed aerobic oxidation of allylic alcohols
with retention of the CÀC double-bond configuration.
We initially tried this oxidation toward geraniol (E-1a)
using 5 mol % Fe(NO ) 9H O, 3 mol % TEMPO, and
(
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(
3
3
3
2
ꢁ
5 mol % NaCl as catalysts in 1,2-dichloethane (Table1,
entry 1). It is interesting to observe that the issue of
isomerization is concentration dependent: when the sub-
strate concentration was reduced to 0.1 mol/L, no isomer-
ization was observed (Table 1, entries 6À9). At a higher
concentration, serious E to Z isomerization was observed
(Table 1, entries 1À5). For considering conversion and
extent of E/Z-isomerization, we have defined 10 mol %
each of Fe(NO ) 9H O, TEMPO, and NaCl in DCE
9) (a) Meng, Q.-H.; Feng, J.-C.; Bian, N.-S.; Liu, B.; Li, C.-C. Synth.
Commun. 1998, 28, 1097. (b) Bora, U.; Chaudhuri, M. K.; Dey, D.;
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(
1
7
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3
3
2
3
(
(
(
0.1 mol/L of substrate) as standard reaction conditions
Table 1, entry 9).
Changing the loading of NaCl does not affect the E/Z
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ratio of the product (Table 2, entries 2À5). As a compar-
sion, when the reaction was conducted in the absence of
NaCl, only 49% of E-2a was obtained with 25% recovery
of E-1a even with a prolonged reaction time of 24 h
(Table 2, entry 1). The exact role of NaCl is still not clear;
(
12) (a) Lin, C.-K.; Lu, T.-J. Tetrahedron 2010, 66, 9688. (b) Chakor,
N. S.; Musso, L.; Dallavalle, S. J. Org. Chem. 2009, 74, 844.
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(
Y.; de las Heras, M. A.; Vaquero, J. J.; Garcia-Navio, J. L.; Alvarez-
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28a
however, as noted in the previous report, we believe that
it may be acting as a ligand to iron.
(14) For such oxidations with MnO
2
, see: (a) Domınguez, M.;
´
ꢁ
Alvarez, R.; Borr ꢂa s, E.; Farr ꢁe s, J.; Pars, X.; de Lera, A. R. Org. Biomol.
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S.; Masuda, T.; Takeda, A. J. Org. Chem. 1982, 47, 4478.
Allylic alcohols without such an issue could also be
oxidized to the corresponding aldehydes/ketones in mod-
erate to good yield (Table 3, entries 8À10). Farnesol
(2E,6E-1k, E/Z = 90:10), an acyclic sesquiterpene alcohol
(
15) For such oxidations with hypervalent iodine compounds, see: (a)
Xue, H.; Gopal, P.; Yang, J. J. Org. Chem. 2012, 77, 8933. (b) Martınez-
Bescos, P.; Cagide-Fagın, F.; Roa, L. F.; Ortiz-Lara, J. C.; Kierus, K.;
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Y.; Ogawa, M. J. Org. Chem. 1987, 52, 4855.
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´
´
B
Org. Lett., Vol. XX, No. XX, XXXX

a
Table 1. Optimization of the Reaction Conditions
Table 3. Substrate Scope of Fe(NO3)3 9H O/TEMPO/NaCl-
2
Catalyzed Room Temperature Aerobic Oxidation of Allylic
Alcohols
3
b
entry
conc (mol/L)
time (h)
yield of 2a (%)
E/Z
1
2
3
4
5
6
7
5.0
2.0
1.0
0.5
0.2
0.1
0.05
0.1
0.1
12
12
12
12
12
12
12
24
3
98 (0)
80/20
89/11
90/10
91/9
93/7
97/3
97/3
97/3
97/3
98 (0)
68 (32)
33 (51)
22 (59)
22 (66)
19 (72)
44 (50)
95 (0)
c
8
d
9
a
The reaction was conducted using 10 mmol of E-1a, 5 mol %
9H O, 3 mol % TEMPO, and 5 mol % NaCl in DCE;
H NMR yield of 2a with recovery of the alcohol in the parentheses;
Fe(NO
3
)
3
2
3
b 1
c
3 3
The reaction was conducted using 1 mmol of E-1a, 5 mol % Fe(NO )
3
d
9
2
H O, 5 mol % TEMPO, and 10 mol % NaCl in DCE; The reaction
was conducted using 1 mmol of E-1a, 10 mol % Fe(NO
TEMPO, and 10 mol % NaCl in DCE.
3
)
3
3 9H2O, 10 mol %
a
Table 2. Effect of NaCl in the Oxidation of E-1a
a
b
E/Z = 99/1. E/Z = 95/5. The reaction was conducted using
c
5
mol % Fe(NO
3
)
3
3 9H2O, 5 mol % TEMPO, 5 mol % NaCl, 0.25 M in
1
,2-dichloroethane.
b
entry
x
time (h)
yield of 2a (%)
E/Z
corresponding Z-aldehydes Z-2a and Z-2p were obtained
in moderate to good yields (Scheme 1).
To further show the practicality and efficiency of this
catalytic system, a 0.1 mol reaction of E-1a was conducted
under the optimized conditions to give E-2a in 90% isolated
yield in 6 h without changing the E/Z ratio (Scheme 2) .
1
2
3
4
5
0
24
4
49 (25)
95 (0)
95 (0)
95 (0)
95 (0)
97/3
97/3
97/3
97/3
97/3
5
10
15
20
3
3
3
a
The reaction was conducted using 1 mmol of E-1a, 10 mol %
9H O, 10 mol % TEMPO, and x mol % NaCl in DCE;
H NMR yield of 2a with recovery of the alcohol in the parentheses.
Fe(NO
3
)
3
2
3
b 1
Scheme 1. Iron-Catalyzed Aerobic Oxidation of Acyclic
Z-Allylic Alcohols
that was extracted from many essential oils, could be
oxidized under these conditions to afford the correspond-
ing product with 66% yield with retention of the CdC
bond configuration (Table 3, entry 11); allylic alcohols
with conjugated as well as unconjugated diene moieties
E-1l and 2E,4E-1m could also be oxidized to the corre-
sponding aldehydes with good yield without changing
the E/Z ratio (Table 3, entries 12 and 13). In addition, as
expected, cyclic allylic alcohol 1n and primary alcohols
with two CdC bonds 1o could also be oxidized to the
corresponding ketone 2n and aldehyde 2o in moderate to
good yields (Table 3, entries 14 and 15).
Interestingly, when Z-allylic alcohols Z-1a and Z-1n
were oxidized under this set of standard conditions, the
In conclusion, we have developed a mild and eco-
friendly protocol for the aerobic oxidation of allylic
Org. Lett., Vol. XX, No. XX, XXXX
C

studies including the synthesis application are being pur-
sued in our laboratory.
Scheme 2. 0.1 mol Scale Oxidation of E-1a
Acknowledgment. We greatly acknowledge the finan-
cial support from the National Basic Research Program of
China (2009CB825300) and the NSF of China (2123006).
We thank Binjie Guo in our group for reproducing the results
of entries 4, 9, and 14 in Table 3 presented in this study.
Supporting Information Available. Experimental proce-
dure and spectroscopic data for products. This material is
available free of charge via the Internet at http://pubs.acs.org.
alcohols using Fe(NO ) 9H O/TEMPO/NaCl as catalyst
3
3
3
2
in DCE to synthesize R,β-unsaturated enals or enones with
retention of the CÀC double bond configuration. Further
The authors declare no competing financial interest.
D
Org. Lett., Vol. XX, No. XX, XXXX