pubs.acs.org/joc
SCHEME 1. Applications of HTIBs in Organic Synthesis
Facile Synthesis of Koser’s Reagent and Derivatives
from Iodine or Aryl Iodides
†
Eleanor A. Merritt, Vania M. T. Carneiro,
†,‡
^
Luiz F. Silva Jr.,‡ and Berit Olofsson*,†
†Department of Organic Chemistry, Arrhenius Laboratory,
Stockholm University, SE-106 91 Stockholm, Sweden, and
‡
´
~
Instituto de Quımica, Universidade de Sao Paulo,
Av. Prof. Lineu Prestes, 748, CP 26077, CEP 05513-970
~
Sao Paulo SP, Brazil
R-Tosyloxy ketones are important synthetic intermediates
in the synthesis of heterocycles, enediynes, and natural
products.9,10 Recently, the use of chiral HTIBs has been
reported, as well as catalytic applications.11-13
Received June 23, 2010
Substituted versions of HTIB (i.e., [hydroxy(tosyloxy)-
iodo]arenes 1) and perfluorinated analogues are useful to
vary the reactivity of the reagent14-16 and to synthesize sub-
stituted diaryliodonium17-22 and alkynyl(aryl)iodonium
salts.23,24
Synthetic routes to [hydroxy(tosyloxy)iodo]arenes usually
consist of two steps, with initial oxidation of an iodoarene to
give the corresponding (diacetoxyiodo)arene or a similar
iodine(III) species, and subsequent treatment with p-tolue-
nesulfonic acid (TsOH) to give the target compound.1 Togo
and co-workers recently reported a one-pot synthesis, where
iodoarenes were treated with m-chloroperbenzoic acid
(mCPBA) at room temperature in chloroform to give HTIBs
inhighyields.25 The samegroup hasalsoreportedthecatalytic
formation of HTIBs, using similar conditions, in R-tosyloxy-
lation of carbonyl compounds.12,13 Another one-pot protocol
involves the oxidant Selectfluor.26
The first one-pot synthesis of neutral and electron-rich
[hydroxy(tosyloxy)iodo]arenes (HTIBs) from iodine and
arenes is presented, thereby avoiding the need for expen-
sive iodine(III) precursors. A large set of HTIBs, includ-
ing a polyfluorinated analogue, can be obtained from the
corresponding aryl iodide under the same conditions. The
reaction proceeds under mild conditions, without excess
reagents, and is fast and high-yielding. Together, the two
presented routes give access to a wide range of HTIBs,
which are useful reagents in a variety of synthetic trans-
formations.
During our ongoing investigations into efficient one-pot
routes to iodonium salts,27-33 we have found conditions that
allow fast and efficient synthesis of Koser’s reagent, and
(11) Altermann, S. M.; Richardson, R. D.; Page, T. K.; Schmidt, R. K.;
Holland, E.; Mohammed, U.; Paradine, S. M.; French, A. N.; Richter, C.;
Bahar, A. M.; Witulski, B.; Wirth, T. Eur. J. Org. Chem. 2008, 5315–5328.
(12) Yamamoto, Y.; Togo, H. Synlett 2006, 798–800.
(13) Tanaka, A.; Togo, H. Synlett 2009, 3360–3364.
(14) Nabana, T.; Togo, H. J. Org. Chem. 2002, 67, 4362–4365.
(15) Zhdankin, V. V.; Kuehl, C. J.; Simonsen, A. J. J. Org. Chem. 1996,
61, 8272–8276.
(16) Zagulyaeva, A. A.; Yusubov, M. S.; Zhdankin, V. V. J. Org. Chem.
2010, 75, 2119–2122.
(17) Ito, M.; Ogawa, C.; Yamaoka, N.; Fujioka, H.; Dohi, T.; Kita, Y.
Molecules 2010, 15, 1918–1931.
Hypervalent iodine reagents have recently found extensive
use as mild oxidants in organic synthesis.1-3 Iodine(III) com-
pounds like (diacetoxyiodo)benzene and [hydroxy(tosyloxy)-
iodo]benzene (HTIB, Koser’s reagent) are employed in a wide
range of transformations, including oxidation of olefins, ring
contractions and expansions, dearomatization of phenols, syn-
thesis of iodonium salts, and R-oxidation of carbonyl com-
pounds (Scheme 1).1,4-8
(18) Dohi, T.; Ito, M.; Morimoto, K.; Minamitsuji, Y.; Takenaga, N.;
Kita, Y. Chem. Commun. 2007, 4152–4154.
(1) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299–5358.
(2) Varvoglis, A. Hypervalent Iodine in Organic Synthesis; Academic Press:
San Diego, CA,1997.
(3) HypervalentIodine Chemistry;Wirth, T., Ed.;Springer:Berlin, Germany,
2003.
(4) Merritt, E. A.; Olofsson, B. Angew. Chem., Int. Ed. 2009, 48, 9052–
9070.
(5) Koser, G. F. Aldrichim. Acta 2001, 34, 89–102.
(6) Moriarty, R. M.; Vaid, R. K.; Koser, G. F. Synlett 1990, 365–383.
(7) Kita, Y.; Morimoto, K.; Ito, M.; Ogawa, C.; Goto, A.; Dohi, T. J. Am.
Chem. Soc. 2009, 131, 1668–1669.
(19) Dohi, T.; Yamaoka, N.; Kita, Y. Tetrahedron 2010, 66, 5775–5785.
(20) Margida, A. J.; Koser, G. F. J. Org. Chem. 1984, 49, 3643–3646.
(21) Koser, G. F.; Wettach, R. H.; Smith, C. S. J. Org. Chem. 1980, 45,
1543–1544.
(22) Carroll, M. A.; Pike, V. W.; Widdowson, D. A. Tetrahedron Lett.
2000, 41, 5393–5396.
(23) Rebrovic, L.; Koser, G. F. J. Org. Chem. 1984, 49, 4700–4702.
(24) Zhdankin, V. V.; Stang, P. J. Tetrahedron 1998, 54, 10927–10966.
(25) Yamamoto, Y.; Togo, H. Synlett 2005, 2486–2488.
(26) Ye, C.; Twamley, B.; Shreeve, J. M. Org. Lett. 2005, 7, 3961–3964.
(27) Bielawski, M.; Olofsson, B. Chem. Commun. 2007, 2521–2523.
(28) Bielawski, M.; Zhu, M.; Olofsson, B. Adv. Synth. Catal. 2007, 349,
2610–2618.
(8) Silva, L. F., Jr. Molecules 2006, 11, 421–434.
(9) Nicolaou, K. C.; Montagnon, T.; Ulven, T.; Baran, P. S.; Zhong,
Y. L.; Sarabia, F. J. Am. Chem. Soc. 2002, 124, 5718–5728.
(10) Rebrovic, L.; Koser, G. F. J. Org. Chem. 1984, 49, 2462–2472.
(29) Zhu, M.; Jalalian, N.; Olofsson, B. Synlett 2008, 592–596.
(30) Bielawski, M.; Aili, D.; Olofsson, B. J. Org. Chem. 2008, 73, 4602–4607.
7416 J. Org. Chem. 2010, 75, 7416–7419
Published on Web 10/06/2010
DOI: 10.1021/jo101227j
r
2010 American Chemical Society