Hypervalent iodine in synthesis. 61. Regeneration of carbonyl function from carbonyl derivatives using polymer-supported phenyliodine BIS(trifluoroacetate)

Article abstract of DOI:10.1081/SCC-100108235

Polymer-supported phenyliodine bis(trifluoroacetate) was prepared and used in the regeneration of carbonyl function from carbonyl derivatives.

Full text of DOI:10.1081/SCC-100108235

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HYPERVALENT IODINE IN SYNTHESIS. 61.
REGENERATION OF CARBONYL FUNCTION FROM
CARBONYL DERIVATIVES USING POLYMER-SUPPORTED
PHENYLIODINE BIS(TRIFLUOROACETATE)
Da-Jun Chen a , Dong-Ping Cheng a & Zhen-Chu Chen b
a Department of Chemistry , Zhejiang University at Xixi Campus , Hangzhou, 310 028, P.
R. China
b Department of Chemistry , Zhejiang University at Xixi Campus , Hangzhou, 310 028, P.
R. China
Published online: 09 Nov 2006.
To cite this article: Da-Jun Chen , Dong-Ping Cheng & Zhen-Chu Chen (2001) HYPERVALENT IODINE IN SYNTHESIS. 61.
REGENERATION OF CARBONYL FUNCTION FROM CARBONYL DERIVATIVES USING POLYMER-SUPPORTED PHENYLIODINE
BIS(TRIFLUOROACETATE), Synthetic Communications: An International Journal for Rapid Communication of Synthetic
Organic Chemistry, 31:24, 3847-3850, DOI: 10.1081/SCC-100108235
To link to this article: http://dx.doi.org/10.1081/SCC-100108235
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SYNTHETIC COMMUNICATIONS, 31(24), 3847–3850 (2001)
HYPERVALENT IODINE IN SYNTHESIS.
61. REGENERATION OF CARBONYL
FUNCTION FROM CARBONYL
DERIVATIVES USING POLYMER-
SUPPORTED PHENYLIODINE
BIS(TRIFLUOROACETATE)
Da-Jun Chen, Dong-Ping Cheng,
and Zhen-Chu Chen*
Department of Chemistry, Zhejiang University at
Xixi Campus, Hangzhou, 310 028, P. R. China
ABSTRACT
Polymer-supported phenyliodine bis(trifluoroacetate) was pre-
pared and used in the regeneration of carbonyl function from
carbonyl derivatives.
In this communication, we wish to report our results concerning the
preparation and synthetic application of polymer-supported phenyliodine
bis(trifluoroacetate) (PPIB).1
Phenyliodine bis(trifluoroacetate) (PIB), which is more reactive than
phenyliodine diacetate (PID), has found wide synthetic utility as effective
oxidizer. For the preparation of PIB, a practical method involves the
ligand – exchange reaction of PID with trifluoroacetic acid.2 Thus, an access
*Corresponding author.
3847
Copyright & 2001 by Marcel Dekker, Inc.
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CHEN, CHENG, AND CHEN
to PPIB might be provided by translation of this conversion into a poly-
meric version. We first prepared PPID by our previously reported method3
and subsequently treated it with trifluoroacetic acid. The resulting resin was
characterised by IR to observe the desired functional conversion. As a
result, the shift of carbonyl adsorption peaks from 1645 cmÀ1 to
1680 cmÀ1, which corresponds exactly to the same spectroscopic feature of
PID and PIB respectively, clearly indicated the successful preparation of the
expected PPIB. Meanwhile, the resin was assayed by iodometry and offered
a 2.10 mmol/g capacity of functional group.
To exploit the useful oxidative property of the prepared resin, it was
employed to effect the transformation of ketonic carbonyl derivatives to
their parent ketones. Recent advances in hypervalent iodine chemistry
have revealed that phenyliodine dicarboxylates serve as efficient tools for
this conversion under mild and non acidic condition.4
In fact, stirring a mixture of PPIB and carbonyl derivatives of ketones
in aqueous THF at room temperature readily achieved the oxidative rege-
neration of carbonyl function in substrate molecules. The reaction offered
mild condition, simple manipulation, high yield and general applicability to
phenylhydrazones, oximes, semicarbazones and tosylhydrazones of aro-
matic or aliphatic ketones.
After the reaction, the resulting iodinated polystyrene was recovered
by filtration and retreated with peracetic acid and trifluoroacetic acid. The
regenerated PPIB possessed the same reactivity as the original one, since the
oxidation reaction could be repeated without significant negative effect.
EXPERIMENTAL SECTION
All carbonyl derivatives were prepared by literature procedure5 and
identified by mp.

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HYPERVALENT IODINE IN SYNTHESIS. 61
Table 1. Regeneration of Ketones with PPIB
3849
Entry
R1
R2
R
Time (min)
Yielda,b (%)
1
2
3
4
5
Ph
Ph
CH3
CH3
CH3
CH3
CH3
CH3
Ph
PhNH
PhNH
PhNH
PhNH
PhNH
PhNH
PhNH
PhNH
OH
OH
NHC(O)NH2
NHC(O)NH2
NHC(O)NH2
NHTs
40
40
45
45
45
45
45
45
50
50
50
40
50
25
25
83
79c
86
85
91
90
93
81
73
64
82
76
71
88
85
p-Cl-Ph
p-Br-Ph
p-CH3-Ph
p-CH3O-Ph
Ph
6
7
8-(CH
9
2)5-
/
Ph
CH3
/
CH3
Ph
10
11
12
13
14
15
-(CH2)5-
Ph
Ph
-(CH2)5-
Ph
-(CH2)5-
/
CH3
/
NHTs
aAll compounds were confirmed by IR, 1H-NMR in comparison with authentic
b
samples. Isolated yields. Regenerated PPIB was employed in this case.
c
Preparation of PPIB: To a mixture of 5 g PPID in 40 mL CH2Cl2, 5 g
trifluoroacetic acid were added with stirring. The mixture gradually became
a dark reddish solution, and stirring was continued overnight. Ether was then
introduced to precipitate the polymer species. The resulting resin was sepa-
rated by filtration, washed with ether and dried to give 5.3 g PPIB. IR (KBr):
2920,1680,1485,1410,1180,1005,820 cmÀ1 functionalcapacity:2.10 mmol/g.
General Oxidation Procedure: 1 g PPIB was dissolved in 10 mL THF,
then 0.3 mL H2O and 1 mmol carbonyl derivative were added. The mixture
was stirred until no starting material was detected by TLC. H2O (15 mL)
was added to precipitate the spent polymer. After removal of the polymer
specie by filtration, the filtrate was extracted with CH2Cl2 (10 mL Â 3), then
washed with 5% aq. Na2CO3 (10 mL Â 2) and H2O (10 mL Â 2) respectively.
The organic layer was dried with MgSO4 and evaporated in vacuo to yield
the desired ketones. Further purification would be achieved by plate chro-
matography if necessary.
REFERENCES
1. Although polymer-supported phenyliodine bis(trifluoroacetate) has
been mentioned, there has been no description of its preparation and

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CHEN, CHENG, AND CHEN
application up to now. Ley, S.V.; Thomas, A.W.; Finch, H. J. Chem.
Soc. Perkin Trans. 1 1999, 669.
2. Spyroudis, S.; Varvoglis, A. Synthesis 1975, 445.
3. Wang, G.P.; Chen, Z.C. Synth. Commun. 1999, 23, 2859.
4. (a) Barton, D.H.R.; Jaszberenyi, J.C.; Shinada, T. Tetrahedron Lett.
1993, 34, 7191. (b) Moriarty, R.M.; Prakash, O.; Vavilikolanu, P.R.
Synth. Commun. 1986, 16, 1247. (c) Chen, D.W.; Chen, Z.C.
Synthesis 1994, 773. (d) Zeng, H.; Chen, Z.C. Synth. Commun. 1993,
23, 2497.
5. Vogel, A.I. Vogel’s Textbook of Practical Organic Chemistry, 4th ed.,
Longman: London, 1978, 1112.
Received in the Netherlands February 9, 2001

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