1
954
J.-M. Chen et al. / Tetrahedron Letters 52 (2011) 1952–1955
Table 2
separated from the reaction mixtures by simple filtration and
TEMPO-catalyzed oxidation of alcohols using PS-DCIB 2a
converted back to PS-DCIB by treatment with aqueous NaOCl/HCl
in about 90% overall yield. The recycled PS-DCIB does not show
any significant loss of activity in oxidation of benzyl alcohol to
benzaldehyde after three regeneration cycles (Table 2, entry 2).
In summary, we have developed a facile one-pot procedure for
the preparation of a recyclable polymer-supported hypervalent
iodine reagent, PS-DCIB, from polystyrene, iodine, and bleach
under mild condition. The synthesis of PS-DCIB employs commer-
cially available chemicals and affords PS-DCIB with high loading le-
OH
2, Py, TEMPO (0.1 equiv)
MeCN-H O(1:1, v/v), 50 oC
O
R1
R2
R1
R2
2
13a-k
14a-k
isolated as 2,4-dinitrophenylhydrazones)
(
Entry
Alcohol 13
Productb
Time (h)
Yieldc,d (%)
Ph
Ph
OH
OH
1
2
14a
3
3
92
1
1
3a
3a
2
vel of active chlorine (loading of –ICl up to 1.35 mmol/g). PS-DCIB
14a
91, 90, 90e
selectively oxidizes primary and secondary alcohols to the respec-
tive carbonyl compounds in the presence of catalytic amount of
TEMPO in aqueous acetonitrile, and selectively chlorinates various
O N
2
3
4
5
OH
OH
14b
14c
14d
2
90
88
organic substrates, including
a-chlorination of carbonyl com-
1
3b
pounds, electrophilic chlorination of electron-rich arenes, and the
chlorination of alkenes under mild conditions with easy work-up.
The reduced form of PS-DCIB, PS-IB can be separated from the
reaction mixtures by simple filtration and converted back to
PS-DCIB by treatment with bleach and aqueous HCl in about 90%
overall yield.
MeO
2.5
1
3c
12
20f
S
OH
1
3d
Acknowledgments
Ph
OH
6
7
14e
14f
12
12
85
82
1
3e
Jiang-Min Chen thanks the financial Foundation of Jiaxing
University for supporting his visit to the University of Minnesota
Duluth. This work was supported by a research grant from the
National Science Foundation (CHE-1009038).
OH
1
3f
OH
8
9
14g
14h
2
92
85
13g
Supplementary data
OH
Supplementary data (experimental procedures and 1H and 13
C
3
3
13h
OH
1
0
1
14i
14j
90
83
Ph
Ph
References and notes
13i
1.
For books and selected reviews on hypervalent iodine chemistry, see: (a)
Varvoglis, A. Hypervalent Iodine in Organic Synthesis; Academic Press: London,
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Koser, G. F. Aldrichim. Acta 2001, 34, 89–102; (d) Koser, G. F. Adv. Heterocycl.
Chem. 2004, 86, 225–292; (e) Moriarty, R. M. J. Org. Chem. 2005, 70, 2893–2903;
1
OH
3j
3.5
1
OH
(
f) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299–5358; (g) Ladziata, U.;
1
2
14k
3
83
Zhdankin, V. V. ARKIVOC 2006(ix), 26–58; (h) Ciufolini, M. A.; Braun, N. A.;
Canesi, S.; Ousmer, M.; Chang, J.; Chai, D. Synthesis 2007(ix), 3759–3772; (i)
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1
3k
a
All reactions of alcohols 13 (0.2 mmol) were performed at 50 °C in the presence
of TEMPO (0.1 equiv), pyridine (3 equiv) and PS-DCIB (1.5 equiv) in MeCN–H
1:1, v/v) (2 mL).
All carbonyl compounds were identified as 2,4-dinitrophenylhydrazone deriv-
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data.
2
O
5
27–537; (m) Quideau, S.; Pouysegu, L.; Deffieux, D. Synlett 2008, 467–495; (n)
(
Yusubov, M. S.; Zhdankin, V. V. Mendeleev Commun. 2010, 20, 185–191; (o)
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b
1
6
3, 653–658; (r) Yusubov, M. S.; Nemykin, V. N.; Zhdankin, V. V. Tetrahedron
c
Conversions for all reactions were above 99% unless noted otherwise.
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d
e
f
2.
For representative recent examples of chlorinations and oxidations using
(
dichloroiodo)benzene, see: (a) Drose, P.; Crozier, A. R.; Lashkari, S.;
Gottfriedsen, J.; Blaurock, S.; Hrib, C. G.; Maichle-Moessmer, C.; Schaedle, C.;
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polymer-supported reagent 2 can be used for efficient oxidation of
various alcohols to the corresponding carbonyl compounds under
mild conditions. Benzylic alcohols are oxidized to the correspond-
ing aldehydes with 100% conversion after 2–3 h (Table 2, entries
8427; (d) Li, X.-Q.; Wang, W.-K.; Zhang, C. Adv. Synth. Catal. 2009, 351, 2342–
2350; (e) Weigand, J. J.; Burford, N.; Davidson, R. J.; Cameron, T. S.; Seelheim, P. J.
Am. Chem. Soc. 2009, 131, 17943–17953; (f) Yu, J.; Zhang, C. Synthesis 2009,
2324–2328; (g) Powers, D. C.; Ritter, T. Nat. Chem. 2009, 1, 302–309; (h)
1
–4), while 2-thiophenemethanol shows much lower reactivity
Whitfield, S. R.; Sanford, M. S. Organometallics 2008, 27, 1683–1689; (i) Kalyani,
D.; Sanford, M. S. J. Am. Chem. Soc. 2008, 130, 2150–2151; (j) Zhao, X.-F.; Zhang,
C. Synthesis 2007, 551–557; (k) Salamant, W.; Hulme, C. Tetrahedron Lett. 2006,
(
entry 5). Primary aliphatic alcohols, 1-octanol and 3-phenyl-1-
propanol are smoothly oxidized to the corresponding aldehydes
in excellent yields (entries 6 and 7), and secondary alcohols (en-
tries 8–12) are oxidized to the respective ketones in good yields.
The byproduct, polystyrene-supported iodobenzene (PS-IB), is
4
7, 605–609; (l) Jin, L.-M.; Yin, J.-J.; Chen, L.; Guo, C.-C.; Chen, Q.-Y. Synlett 2005,
893–2898; (m) Yusubov, M. S.; Drygunova, L. A.; Tkachev, A. V.; Zhdankin, V. V.
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2