C O M M U N I C A T I O N S
Table 1. Oxidative Cleavage of Olefins with Iodosylbenzene
Scheme 2
R (reaction time h, yield): H (1, 89%), p-Me (2, 57%)), p-Cl (5, 75%),
m-CF3 (6, 69%), p-CF3 (8, 70%), p-MeO2C (5.5, 64%), m-NO2 (42, 88%).
under the conditions similar to method B and aromatic aldehydes
were obtained in good yields (Scheme 2).19,20
In summary, we have developed an efficient method for the
oxidative cleavage of carbon-carbon double bonds as a safety
alternative to ozonolysis, by using a combination of iodosylbenzene
and HBF4 in the presence of water.
Supporting Information Available: Experimental details and
Figures S1-S4. This material is available free of charge via the Internet
References
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(2) For two-step cis-dihydroxylation of alkenes with PhI(OCOCF3)2, see:
Celik, M.; Alp, C.; Coskun, B.; Gultekin, M. S.; Balci, M. Tetrahedron
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See: (a) Frohn, H. J.; Pahlmann, W. J. Fluorine Chem. 1985, 28, 191.
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a See text. b Yields of carbonyl compounds were determined by 1H NMR.
Parentheses are isolated yields of alcohols (or their derivatives), after
reduction with NaBH4 in MeOH. c Yields of byproduct 4b: 17% (entry 9)
and 38% (entry 10). d Olefin 3d (46%) was recovered. e Isolated as 2,4-
(dinitrophenyl)hydrazone. f Yields of phenylacetaldehydes: 85%, 24%, 21%,
32%, and 8% for entries 18-22.
(9) (a) Ochiai, M.; Miyamoto, K.; Shiro, M.; Ozawa, T.; Yamaguchi, K. J.
Am. Chem. Soc. 2003, 125, 13006. (b) Ochiai, M.; Miyamoto, K.; Yokota,
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M. Coord. Chem. ReV. 2006, 250, 2772.
Cyclic (cyclopentenes, cyclohexenes, etc., entries 1-6) and
acyclic (entries 15-17) olefins are cleaved smoothly under our
conditions. With styrene, however, 1,2-phenyl migration yielding
phenylacetaldehyde was proved to be a principal reaction pathway
(entry 18), as reported by Moriarty and Koser.10,17 In contrast,
electron-deficient styrenes with CF3, CO2Me, and NO2 groups
primarily undergo the oxidative cleavage yielding substituted
benzaldehydes in good yields, being accompanied by formation of
the rearranged phenylacetaldehydes (entries 19-22). Ratios of the
oxidative cleavage to rearrangement products depend on the
electronic nature of the aryl groups, and a linear Hammett
relationship (F ) 3.1) for the substituent effects with r ) 0.98 was
found between log(kArCHO/kArCH2CHO) and σ values (Figure S2).
The cleavage of m-nitrostyrene is very slow and requires a
prolonged reaction time (3 days, entry 22). Interestingly, formation
of a considerable amount (34%) of the corresponding epoxide
together with m-NO2C6H4CHO (39%) was detected when the
reaction was quenched after 25 h. These results appear to indicate
the intermediacy of epoxides on the way to the formation of the
cleaved products from styrenes at least in part. Iodosylbenzene and
its derivatives transfer the oxygen atom to highly electron-deficient
olefins, affording epoxides.18 In fact, we found that a variety of
aryloxiranes undergo an oxidative cleavage of the epoxide rings
(10) Justik, M. W.; Koser, G. F. Tetrahedron Lett. 2004, 45, 6159.
(11) Zhdankin, V. V.; Tykwinski, R.; Caple, R.; Berglund, B.; Koz’min, A.
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(12) Richter, H. W.; Cherry, B. R.; Zook, T. D.; Koser, G. F. J. Am. Chem.
Soc. 1997, 119, 9614.
(13) Coordination of two water molecules increases the stability of λ3-iodane
1. Two linear hypervalent bondings O-I‚‚‚O and C-I‚‚‚O in 6a are in
the preferred combinations of the ligands in terms of trans influences,
which control the stability of hypervalent bonding of λ3-iodanes. See:
Ochiai, M.; Sueda, T.; Miyamoto, K.; Kiprof, P.; Zhdankin, V. V. Angew.
Chem., Int. Ed. 2006, 45, 8203.
(14) Cativiela, C.; Garcia, J. I.; Mayoral, J. A.; Salvatella, L. Can. J. Chem.
1994, 72, 308.
(15) Taft R value of solvent hydrogen-bond donor acidity of HFIP is 1.96.
See: Reichardt, C. SolVents and SolVent Effects in Organic Chemistry;
Wiley-VCH: Weinheim, Germany, 2003.
(16) Method B possibly generates a tetracoordinated alkoxy-λ3-iodane 6b, being
a more powerful oxidant than hydroxyiodane 6a (Figures S3 and S4).
(17) (a) Moriarty, R. M.; Khosrowshahi, J. S.; Prakash, O. Tetrahedron Lett.
1985, 26, 2961. (b) Rebrovic, L.; Koser, G. F. J. Org. Chem. 1984, 49, 2462.
(18) (a) Moriarty, R. M.; Gupta, S. C.; Hu, H.; Berenschot, D. R.; White, K.
B. J. Am. Chem. Soc. 1981, 103, 686. (b) Ochiai, M.; Nakanishi, A.;
Suefuji, T. Org. Lett. 2000, 2, 2923. (c) McQuaid, K. M.; Pettus, T. R. R.
Synlett 2004, 2403.
(19) For cleavage of 2-phenyloxirane with [bis(trifluoroacetoxy)iodo]benzene,
see: Spyroudis, S.; Varvoglis, A. J. Org. Chem. 1981, 46, 5231.
(20) The oxidative cleavage of aryloxiranes probably proceeds via the acid-
catalyzed formation of intermediate Vic-diols.
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