J. M. Goff et al. / Tetrahedron Letters 42 (2001) 5597–5599
5599
reactions with hypervalent iodine reagents will be pre-
sented in a full report.
dride (g-branching) gave a 41% yield and 3-methylbu-
tanoic anhydride (b-branching) gave a 20% yield of the
corresponding products. 3,3-Dimethylbutanoic anhy-
dride failed to give a 2-tosyloxycarboxylate ester with
HTIB. 2-Methylpropanoic anhydride (a-branching)
also gave no tosylate derivative with HTIB; in this case
methyl methacrylate was produced and isolated as the
dibromo adduct in 9% yield.
References
1. Johnson, J. R. Org. React. 1942, 1, 210–302.
2. House, H. O. Modern Synthetic Reactions, 2nd ed.; W. A.
Benjamin: Menlo Park, CA, 1972; pp. 660–662.
3. Deno, N. C.; Billups, W. E.; DiStefano, R. E.; McDon-
ald, K. M.; Schneider, S. J. Org. Chem. 1970, 35, 278–
279.
4. (a) Tamura, Y.; Wada, A.; Sasho, M.; Kita, Y. Tetra-
hedron Lett. 1981, 22, 4283–4286; (b) Tamura, Y.; Wada,
A.; Sasho, M.; Fukunaga, K.; Maeda, H.; Kita, Y. J.
Org. Chem. 1982, 47, 4376–4378.
An attempt to oxytosylate succinic anhydride (melt, ca.
135°C) with HTIB was unsuccessful. However, when
the intermolecular anhydride of methyl hydrogen succi-
nate was treated sequentially with HTIB and MeOH/
TsOH, dimethyl 2-tosyloxysuccinate was isolated in
30.5% yield.
5. (a) Horeau, A. Tetrahedron Lett. 1962, 965–969; (b)
Weidmann, R.; Horeau, A. Bull. Soc. Chim. Fr. 1967,
117–124.
Based on earlier studies of the oxysulfonylation of
ketones, b-dicarbonyl compounds, and silyl enol ethers
with iodine(III) sulfonate reagents,8,9 the oxytosylation
of anhydrides at a-carbon with HTIB is consistent with
enolic behavior in the anhydrides and the intermediate
formation of 2-phenyliodonio- and/or O-phenyliodonio
tosylates, 10 and 11. SN2 or SN2% displacement of
iodobenzene by the tosylate ion in such intermediates
would afford 2-tosyloxyalkanoic anhydrides.
6. Hendon, J. E.; Gordon, A. W.; Gordon, M. J. Org.
Chem. 1972, 37, 3184–3185.
7. Brown, H. C.; Dhar, R. K.; Ganesan, K.; Singaram, B. J.
Org. Chem. 1992, 57, 499–504.
8. (a) Koser, G. F.; Relenyi, A. G.; Kalos, A. N.; Rebrovic,
L.; Wettach, R. H. J. Org. Chem. 1982, 47, 2487–2489;
(b) Zefirov, N. S.; Zhdankin, V. V.; Dan’kov, Yu. V.;
Koz’min, A. S.; Chizov, O. S. J. Org. Chem. USSR (Engl.
Transl.) 1985, 21, 2252–2253 (Plenum, 1986), Zh. Org.
Khim. 1985, 2461–2462; (c) Lodaya, J. S.; Koser, G. F. J.
Org. Chem. 1988, 53, 210–212; (d) Moriarty, R. M.; Vaid,
R. K.; Ravidumar, V. T.; Vaid, B. K.; Hopkins, T. E.
Tetrahedron 1988, 44, 1603–1607; (e) Hatzigrigoriou, E.;
Varvoglis, A.; Bakola-Christianopoulou, M. J. Org.
Chem. 1990, 55, 315–318; (f) Tuncay, A.; Dustman, J. A.;
Fisher, G.; Tuncay, C. I.; Suslick, K. S. Tetrahedron Lett.
1992, 33, 7647–7650.
9. (a) Moriarty, R. M.; Penmasta, R.; Awasthi, A. K.; Epa,
W. R.; Prakash, I. J. Org. Chem. 1989, 54, 1101–1104; (b)
Moriarty, R. M.; Epa, W. R.; Penmasta, R.; Awasthi, A.
K. Tetrahedron Lett. 1989, 30, 667–670.
10. (a) Hoffman, R. V.; Kim, H.-O. J. Org. Chem. 1988, 53,
3855–3857; (b) Hoffman, R. V.; Kim, H.-O. Tetrahedron
Lett. 1990, 31, 2953–2956; (c) Hoffman, R. V.; Kim,
H.-O.; Wilson, A. L. J. Org. Chem. 1990, 55, 2820–2822;
(d) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48,
3007–3020; (e) Hoffman, R. V.; Kim, H.-O. Tetrahedron
Lett. 1993, 34, 2051–2054; (f) Hoffman, R. V.; Kim,
H.-O. J. Org. Chem. 1995, 60, 5107–5113; (g) Hoffman,
R. V.; Johnson, M. C.; Okonya, J. F. J. Org. Chem. 1997,
62, 2458–2465.
HTIB undergoes competing decomposition reactions in
carboxylic anhydrides at the temperatures employed for
oxytosylation. For example, although 3,3-dimethylbu-
tanoic anhydride gave no tosylate derivative with
HTIB, the iodane was completely reduced after 30 min
at 94–95°C, the yield of iodobenzene (GC determina-
tion) being 95%. NMR analysis of the reaction mixture
revealed no obvious products of anhydride oxidation.
In another experiment, HTIB (2.0 mmol) was heated
with propionic anhydride (10.0 mmol) for 20 min at
94–95°C. At the end of this time, no oxidant remained
(i.e. negative KI test) and the yield of iodobenzene was
found to be 94%, or 21% higher than the yield of the
ester reported in Table 1. A more complete discussion
of the scope, limitations, and mechanisms of anhydride
.