Y. Masui et al. / Tetrahedron Letters 45 (2004) 1853–1856
1855
amines or high exothermic reaction heat. A cryogenic
reaction temperature confines equipment and signifi-
cantly increases the cost of production. Our new process
allows the use of aqueous amines and requires no
cryogenic temperature. Therefore, the present new pro-
cess is more practical than the conventional one.
to a practical process for the synthesis of the side chain.7
In addition, we already found that alcohols as the sub-
strates can be changed into thiols10 to afford the corre-
sponding sulfamide derivatives as this study. These
results of our further works will be reported separately.
In conclusion, we described a new one-pot process to
produce N-acyl-substituted sulfamides 2 in the presence
of water or in the absence of water in efficient yields
from CSI, alcohols and aqueous or dry amines via the
Burgess-type intermediates 3, which are generated in situ
by the reaction of N-(chlorosulfonyl)carbamates 1 with
tertiary amines.
When dry diethylamine was used in both of our new
process, which proceeded via the Burgess-type interme-
diates 3, and the conventional one which used no ter-
tiary amine, they afforded the target product 2c in the
same yield (Table 1, entries 12 vs 13).
Solvent, which does not react with CSI at 0 °C, must be
chosen. Ethyl acetate (86%, Table 1, entry 4) and ace-
tonitrile (83%, Table 1, entry 5) led to the lower yields
than toluene (90%, Table 1, entry 1). Dichloromethane
gave the target compound 2a in 73% yield (Table 1,
entry 6). Therefore, toluene was chosen as a reaction
solvent.
Acknowledgements
We thank Dr. T. Konoike and Mr. M. Hajima for their
helpful discussion.
Tertiary amines to afford the Burgess-type intermediates
3 influenced the yields for the reaction. When no tertiary
amine was used (a conventional condition), aqueous
methylamine gave the product 2b in 7% yield (Table 1,
entry 8). Pyridine (93%, Table 1, entry 7) and triethyl-
amine (93%, Table 1, entry 9) are preferable. N-Meth-
ylmorpholine provided moderate yield (88%, Table 1,
entry 10). 4-DMAP gave low yield (22%, Table 1, entry
11). Presumably this depends upon the reactivity and
stability of the ammonium intermediates 3.
References and notes
1. (a) Graf, R. German Patent 931467, 1952 (Farbwerke
Hoechst AG); (b) Graf, R. Chem. Zbl. 1955, 11094.
2. (a) Graf, R. Chem. Ber. 1963, 96, 56–67; (b) Picard, J. A.;
OÕBrien, P. M.; Sliskovic, D. R.; Anderson, M. K.;
Bousley, R. F.; Hamelehle, K. L.; Krause, B. R.; Stanfield,
R. L. J. Med. Chem. 1996, 39, 1243–1252; (c) Abdaoui,
M.; Dewynter, G.; Aouf, N.; Favre, G.; Morere, A.;
Montero, J.-L. Bioorg. Med. Chem. 1996, 4, 1227–1235;
(d) Abdaoui, M.; Dewynter, G.; Montero, J.-L. Tetrahe-
The scope of alcohols as substrates is relatively broad.
Primary, secondary and tertiary alcohols gave the target
compounds 2 in high yields. Especially, bulky aliphatic
alcohols such as tert-butanol (Table 1, entries 19 and 20)
and 1-adamantyl alcohol (Table 1, entries 21 and 22)
gave the target compounds in high yields (91–97%).
Phenol and 4-methoxyphenol afforded the correspond-
ing phenoxycarbonylsulfamides 2m and 2o in 67% and
54% yields, respectively (Table 1, entries 23 and 25),
because of its lower nucleophilicity. In cases of prepar-
ing sulfamides 2n and 2p by using aqueous methylamine,
yields were lower than 30% because of a side reaction
replacing the phenoxy anion with methylamino group.
€
dron Lett. 1996, 32, 5695–5698; (e) Regaınia, Z.; Abdaoui,
M.; Aouf, N.-E.; Dewynter, G.; Montero, J.-L. Tetrahe-
dron 2000, 56, 381–387.
3. (a) Graf, R. German Patent 940292, 1952 (Farbwerke
Hoechst AG); (b) Graf, R. Chem. Zbl. 1956, 12973.
4. (a) Atkins, G. M.; Burgess, E. M. J. Am. Chem. Soc. 1968,
90, 4744–4745; (b) Atkins, G. M.; Burgess, E. M. J. Am.
Chem. Soc. 1972, 94, 6135; (c) Burgess, E. M.; Penton, H.
R.; Taylor, E. A. J. Org. Chem. 1973, 38, 26–31; (d)
Burgess, E. M.; Penton, H. R.; Tayler, E. A.; Williams, W.
M. Org. Synth. 1977, 56, 40–43.
5. The use as a dehydrating reagent, see: (a) Miller, C. P.;
Kaufman, D. H. Synlett 2000, 1169–1171; (b) Khapli, S.;
Dey, S.; Mal, D. J. Indian Inst. Sci. 2001, 81, 461–476; (c)
The synthesis of sulfamidates from 1,2-diols, see: Nico-
laou, K. C.; Huang, X.; Snyder, S. A.; Rao, P. B.; Bella,
M.; Reddy, M. V. Angew. Chem., Int. Ed. 2002, 41, 834–
838; (d) The synthesis of nonsymmetrical sulfamides, see:
Nicolaou, K. C.; Longbottom, D. A.; Snyder, S. A.;
Nalbanadian, A. Z.; Huang, X. Angew. Chem., Int. Ed.
2002, 41, 3866–3870; (e) Reaction with alcohol, see:
Wood, M. R.; Kim, J. Y.; Books, K. M. Tetrahedron
Lett. 2002, 43, 3887–3890.
The scope of amines containing active hydrogen as
substrates is relatively broad. Ammonia, primary and
secondary amines gave the target compounds in high
yields. Surprisingly, an aromatic amine such as aniline
(Table 1, entry 16) gave the target compound 2f in 97%
yield, although the reported elemental reaction of ani-
line with Burgess-like reagent 6 at room temperature for
12 h gave N-[(tert-butoxycarbonyl)-N0-phenylsulfamide
(8) in 50% yield.6 A bulky aliphatic amine such as 1-
adamantanamine (Table 1, entry 15) gave the target
compound 2e in 45% yield.
6. Winum, J.-Y.; Toupet, L.; Barragan, V.; Dewynter, G.;
Montero, J.-L. Org. Lett. 2001, 3, 2241–2243.
7. (a) A practical process for the synthesis of compound 2i
was patented, see: Nishino, Y.; Yuasa, T.; Komurasaki,
T.; Kakinuma, M.; Masui, T.; Kobayashi, M. Patent
Disclosure No. JP 2003-26680; (b) Masui, T.; Kabaki, M.;
Watanabe, H.; Kobayashi, T.; Masui, Y., in preparation.
8. A practical process for the synthesis of the side chain
of doripenem was reported. However, in the report,
Further investigation on the generality of the present
reaction is currently underway. On the other hand,
compound 2i is a raw material of the aminosulfamoyl-
containing side chain8 of the novel carbapenem antibi-
otic doripenem hydrate.9 The title reaction was applied