A Mild and Efficient Oxidation of Alcohols to Ketones with Iodosobenzene/(Salen) Manganese Complex

Article abstract of DOI:10.1081/SCC-120026321

An excellent method for the chemoselective oxidation of alcohols to ketones with C₆H₅IO catalyzed by (salen) manganese/4A MS in CH₃CN has been devised. The reported procedure is fast, simple, and the yields are excellent (> 95%) in most cases.

Full text of DOI:10.1081/SCC-120026321

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A Mild and Efficient Oxidation of Alcohols to Ketones
with Iodosobenzene/(Salen) Manganese Complex
Sung Soo Kim# a & Galina Borisova a
a Department of Chemistry and Center for Chemical Dynamics, Inha University, Incheon,
South Korea
Version of record first published: 19 Aug 2006.
To cite this article: Sung Soo Kim# & Galina Borisova (2003): A Mild and Efficient Oxidation of Alcohols to Ketones with
Iodosobenzene/(Salen) Manganese Complex, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 33:22, 3961-3967
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SYNTHETIC COMMUNICATIONSÕ
Vol. 33, No. 22, pp. 3961–3967, 2003
A Mild and Efficient Oxidation of Alcohols to
Ketones with Iodosobenzene/(Salen)
Manganese Complex
,#
Sung Soo Kim and Galina Borisova
*
Department of Chemistry and Center for Chemical
Dynamics, Inha University, Incheon, South Korea
ABSTRACT
An excellent method for the chemoselective oxidation of alcohols to
ketones with C6H5IO catalyzed by (salen) manganese/4 A MS in
CH3CN has been devised. The reported procedure is fast, simple,
and the yields are excellent (>95%) in most cases.
Key Words: Alcohol; Ketone; Chemoselective; Mn(salen); Iodoso-
benzene.
*Correspondence: Sung Soo Kim, Department of Chemistry and Center for
Chemical Dynamics, Inha University, Incheon 402-751, South Korea;
Fax: þ82-32-867-5604; E-mail: sungsoo@inha.ac.kr.
#This article was written during the sabbatical leave of absence.
3961
DOI: 10.1081/SCC-120026321
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
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3962
Kim and Borisova
INTRODUCTION
The oxidation of alcohols to aldehydes and ketones is one of the
most important transformations in organic synthesis.[1] The achiral
chromium(III)[2] and manganese(III)[3] complexes of the salen ligand are
the effective catalysts for the epoxidation of various olefins with iodoso-
benzene as the terminal oxidant. Chiral (salen) manganese catalysts[4,5]
were combined with iodosylbenzene, sodium hypochlorite, or m-chloro-
perbenzoic acid for the enantioselective epoxidation of cis- and trans-
substituted olefins.
E-b-methylstyrene, a trans-olefin[6] undergo asymmetric epoxidation
utilizing (salen) chromium complex/iodosobenzene with triphenylpho-
sphine oxide as the additive. The alcohols[7] were oxidized into aldehydes
and ketones with the hypervalent iodine(III) reagents triggered by var-
ious catalysts. (Salen) chromium(III) catalyzed oxidations of a series of
allylic and benzylic alcohols to corresponding carbonyl compounds[8,9]
have been carried out with either iodosobenzene or iodosobenzene
diacetate as the oxidant. We now report the oxidation of these alcohols
with a new (salen) manganese complex.
RESULTS AND DISCUSSION
N,N 0-bis(3,5-dichlorosalicylidine)-1,2-ethylenediaminomanganese(III)
chloride(I) was synthesized according to the known procedure.[8,10]
Catalyst I is used with C6H5IO as an oxidant under various conditions
for the oxidation of 1-phenylethanol (Table 1).
Comparison of result of entries 1 and 2 indicate that addition of
4 A molecular sieve (MS) improves yield of the ketone. CH3CN appears
to be the best solvent for the oxidation (entries 1, 3–5). Accordingly the
N
O
N
O
+
Mn
Cl
Cl
Cl-
Cl
Cl
Figure 1. I:N,N 0 -bis(3,5-Dichlorosalicylidene)-1,2-ethylenediaminomanganese
(III) chloride (C16H10Cl5N2O2Mn; M.W. 494.47).

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Iodosobenzene/(Salen) Manganese Complex
3963
Table 1. Oxidation of 1-phenylethanol with C6H5IO at r.t. under various
conditions.a
Entry
Catalyst
Additive
Solvent
Time (h)
Yield (%)
1
2
3
4
5
I
I
I
I
I
4 A MS
—
CH3CN
CH3CN
C6H6
2
2
4
4
4
89
82
58
40
62
4 A MS
4 A MS
4 A MS
CH2Cl2
EtOAc
aCatalyst:C6H6IO:additive:solvent ¼ 0.1 mmol:1.5 mmol:0.12 g:4 mL.
OH
(salen)Mn(III)
CH
O
R
R
Ph
Ph
PhI
O
=
PhIO
(salen)Mn(V)
C
Scheme 1.
factors of entry 1 of Table 1 constitute most favorable conditions
for the oxidation. The mechanism of oxidative process is indicated in
Sch. 1.
1-Phenylethanols containing substituents on phenyl ring (entries 1–6)
(Table 2) are efficiently oxidized to corresponding ketones for relatively
short reaction time. The reactions show little substituent effect on the
oxidative process. The change of methyl of 1-phenylethanol to other
larger groups (entries 7–11) hardly influences the reactivity and also the
yield. Only entry 12 gives a little lower yield. Therefore, most of second-
ary benzylic alcohols indicate vigorous reactivity towards oxidation
within relatively short reaction time (yield: 89–99%, reaction time:
1–2 h). Similar secondary benzylic oxidation previously[8] gave only satis-
factory results (yield: 20–69%, reaction time: 14 h). On the contrary,
primary benzylic alcohol (entry 13) takes longer time for the oxidation
to give only poor yield. The reluctance of the reaction has been also
observed for oxidation of allylic alcohol (entry 14).
Present catalytic system is useful for the oxidation of secondary
benzylic alcohols to ketones. However benzylic and allylic alcohols
reveal poor oxidative tendency.

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3964
Kim and Borisova
Table 2. Oxidation of alcohols with [Mn(III)(salen)Cl]/C6H5IO at r.t.
C6H5IO / [Mn(III)(salen)Cl]
4Å MS , CH3CN , r.t.
OH
C
O
C
Ph
R
Ph
R
Substrate
1 mmol
C6H5IO
1.5 mmol
[Mn(III)(salen)Cl]
0.1 mmol
4A MS
0.12 g
CH3CN
4 mL
Entry
1
Substrate
Product
Time (h)
2
Yielda,b (%)
89
OH
O
OH
O
2
3
4
5
2
2
2
2
86
95
97
97
Me
Me
OH
O
MeO
MeO
OH
O
Br
Br
OH
OH
O
Cl
Cl
Cl
O
6
7
1
2
99
99
Cl
OH
OH
O
O
8
9
1
92
99
99
OH
O
1.5
1.5
OH
O
10

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Iodosobenzene/(Salen) Manganese Complex
Table 2. Continued.
Product
3965
Entry
11c
Substrate
Time (h)
1
Yield (%)a,b
89
OH
O
OH
OH
O
12
1
77
O
13
14
18
6
11
67
OH
O
aIsolated yield.
bAll the 1H NMR spectra of ketones and aldehydes exactly match with those
tabulated in the aldrich library of 13C and 1H FT NMR spectra by edited
Charles J. Pouchert, Jacqlynn Behnke.
cN,N - bis(5 - Chlorosalicylidine) - 1,2 ethylenediaminomanganese(III)
chloride.
(C16H12Cl3N2O2Mn; M.W. 425.57) is the catalyst for the oxidation.
EXPERIMENTAL
N,N 0-bis(3,5-Dichlorosalicylidine)-1,2-
ethylenediaminomanganese(III) Chloride
Ethylenediamine (0.300 g, 5 mmol) was added to solution of
3,5-dichlorosalicylaldehyde (1.91 g, 10 mmol) in anhydrous ethanol
(30 mL) in a round-bottom flask equipped with a magnetic bar and
West condenser. The yellow solution was refluxed for 3 h. The reaction
mixture was then allowed to react overnight at ambient temperature. The
mixture was filtered to yield clean bis-(3,5-dichlorosalicylidene)-ethylene-
1
diamine. (Yield: 1.9 g, 94%). H NMR (CDCl3): ꢀ 4.01 (s, 4H, (CH2)2),
7.16 (d, 2H, C6H2), 7.90 (d, 2H, C6H2), 8.28 (s, 2H, (CH)2).
To a suspension of bis-(3,5-dichlorosalicylidene)ethylenediamine
[0.609 g (1.5 mmol)] in absolute ethanol (30 mL) was added suspension
of Mn(OAc)2ꢀ4H2O [0.367 g (1.5 mmol)] in ethanol (30 mL) which were
allowed to reflux in the air for 3 h. Then 3-M-fold quantity of lithium
chloride was added to this solution and was further refluxed for 1 h. The
reaction mixture was left overnight at r.t. and filtered. The filtrate was
dried under reduced pressure to afford 0.69 g of the required complex,

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3966
Kim and Borisova
I (yield: 93%). Anal. calcd. for C16H10Cl5N2O2 Mn: C, 38.86; H, 2.03; N,
5.66. Found: C, 38.54; H, 2.32; N, 5.92.
General Procedure for the Oxidation of the Alcohols with
PhIO Catalyzed by I
To a solution of the substrate (1.00 mmol) in CH3CN (4 mL)
was added 0.1 equiv. of catalyst I, 0.12 g of 4 A MS and 1.5 equiv. of
iodosobenzene. The mixture was stirred for hours and the solvent was
evaporated. The remainder was subject to silica gel column chromato-
graphy with ethyl acetate:hexane (2:8) mixture as eluent. The solvent was
1
removed by evaporation and the products were identified by H NMR
spectroscopy.
ACKNOWLEDGMENT
The authors warmly thank Korea Science and Engineering
Foundation for the financial support (R01-2001-00057). G. Borisova
has been supported by the fund from KISTEP.
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Iodosobenzene/(Salen) Manganese Complex
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Received in Japan May 12, 2003

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