Abstract
A straightforward synthesis of Δ3-cephems 2 bearing heteroatom substituents directly attached to C(3)-position was performed successfully by a sequential addition/cyclization reaction of allenecarboxylate 4 derived from eithen penicillin 1. Upon treatment of the allenecarboxylate 4 with morpholine, pyrrolidine, sodium azide, and 5-methyl-1,3,4-thiadiazole-2-thiol in DMF in the presence of calcium chloride, the addition/cyclization reaction proceeded smoothly to afford the corresponding 3-substituted Δ3-cephems 2a-e. Reaction of the allenecarboxylate 4 with lithium chloride in NMP (N-methyl-2-pyrrolidone) in the presence of aluminum chloride afforded 3-chloro-Δ3-cephem 2f, while without aluminum chloride, 3-phenylsulfonyl-Δ3-cephem 2e was mainly obtained. The 3-sulfenyl-Δ3-cephems 12 were prepared by a similar addition/cyclization reaction of allenecarboxylates 10 with a catalytic amount of thiolates. The sulfenyl moieties attached at the sulfur atom of the C(4)-substituent of 10 were introduced at the C(3)-position of the cephem framework 2.
| Original language | English |
|---|---|
| Pages (from-to) | 3651-3658 |
| Number of pages | 8 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 69 |
| Issue number | 12 |
| DOIs | |
| Publication status | Published - Dec 1996 |
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Transformation of penicillins into 3-substituted Δ3-cephems through addition/cyclization of allenecarboxylates. / Tanaka, Hideo; Sumida, Shin Ichi; Kameyama, Yutaka; Sorajo, Koichi; Wada, Isao; Torii, Sigeru.
In: Bulletin of the Chemical Society of Japan, Vol. 69, No. 12, 12.1996, p. 3651-3658.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Transformation of penicillins into 3-substituted Δ3-cephems through addition/cyclization of allenecarboxylates
AU - Tanaka, Hideo
AU - Sumida, Shin Ichi
AU - Kameyama, Yutaka
AU - Sorajo, Koichi
AU - Wada, Isao
AU - Torii, Sigeru
PY - 1996/12
Y1 - 1996/12
N2 - A straightforward synthesis of Δ3-cephems 2 bearing heteroatom substituents directly attached to C(3)-position was performed successfully by a sequential addition/cyclization reaction of allenecarboxylate 4 derived from eithen penicillin 1. Upon treatment of the allenecarboxylate 4 with morpholine, pyrrolidine, sodium azide, and 5-methyl-1,3,4-thiadiazole-2-thiol in DMF in the presence of calcium chloride, the addition/cyclization reaction proceeded smoothly to afford the corresponding 3-substituted Δ3-cephems 2a-e. Reaction of the allenecarboxylate 4 with lithium chloride in NMP (N-methyl-2-pyrrolidone) in the presence of aluminum chloride afforded 3-chloro-Δ3-cephem 2f, while without aluminum chloride, 3-phenylsulfonyl-Δ3-cephem 2e was mainly obtained. The 3-sulfenyl-Δ3-cephems 12 were prepared by a similar addition/cyclization reaction of allenecarboxylates 10 with a catalytic amount of thiolates. The sulfenyl moieties attached at the sulfur atom of the C(4)-substituent of 10 were introduced at the C(3)-position of the cephem framework 2.
AB - A straightforward synthesis of Δ3-cephems 2 bearing heteroatom substituents directly attached to C(3)-position was performed successfully by a sequential addition/cyclization reaction of allenecarboxylate 4 derived from eithen penicillin 1. Upon treatment of the allenecarboxylate 4 with morpholine, pyrrolidine, sodium azide, and 5-methyl-1,3,4-thiadiazole-2-thiol in DMF in the presence of calcium chloride, the addition/cyclization reaction proceeded smoothly to afford the corresponding 3-substituted Δ3-cephems 2a-e. Reaction of the allenecarboxylate 4 with lithium chloride in NMP (N-methyl-2-pyrrolidone) in the presence of aluminum chloride afforded 3-chloro-Δ3-cephem 2f, while without aluminum chloride, 3-phenylsulfonyl-Δ3-cephem 2e was mainly obtained. The 3-sulfenyl-Δ3-cephems 12 were prepared by a similar addition/cyclization reaction of allenecarboxylates 10 with a catalytic amount of thiolates. The sulfenyl moieties attached at the sulfur atom of the C(4)-substituent of 10 were introduced at the C(3)-position of the cephem framework 2.
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U2 - 10.1246/bcsj.69.3651
DO - 10.1246/bcsj.69.3651
M3 - Article
AN - SCOPUS:0030478250
VL - 69
SP - 3651
EP - 3658
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 12
ER -