80(P08) Uroporphyrinogen I octamethyl esterの異性化反応について(ポスター発表の部)
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At this laboratory, attention has been directed to the chemistry of dipyrromethane synthesis, particularly in regard to development of a method for the effective synthesis of bilane and oligopyrroles related to the interest of the biosynthetic mechanism of uroporphyrinogen III. During investigation on the synthesis of dipyrromethanes under mild and neutral conditions, coupling reaction between α-free pyrrole 2 and 2-mercaptobenzothiazolylmethylpyrrole 1 was found to proceed smoothly at room temperature using a thiophile reagent such as silver (I) trifrate (AgOTf), to give dipyrromethane 3 in excellent yield. This method was successfully utilized for the synthesis of pentapyrrole derivative 18. In addition, we have found that the coupling reaction of dipyrromethane 3 with azafulvenium ion 1', generated from 2-mercaptobenzothiazolylmethylpyrrole derivative 1 and AgOTf in dry benzene at room temperature, gave a symmetric dipyrromethane 20 in high yield. Looking at this rearrangement from 3 into 20 through pyrrolenine intermediate 19, we were fascinated by the extensive studies on the reaction of azafulvenium ion 1' as an electrophilic reagent with tetrapyrrole macrocyclic compound, connecting to the attractive biosynthetic mechanism of uroporphyrinogen III. Teratment of uroporphyrinogen I octamethyl ester with 2-mercaptobenzothiazolylmethylpyrrole derivative 1 and AgOTf under anaerobic condition in dichloromethane for 20h, followed by aerial oxidation of the products, gave a statistical mixture of uroporphyrine I〜IV octamethyl esters. It was proposed that this transformation proceeds through a spiro-pyrrolenine as a key intermediate, which is very close to the remarkable rearrangement reaction demonstrated by Battersby as a model for the biosynthesis of uroporphyrinogen III. Recently, we also found the same result from the cyclization raction of pentapyrrole derivative 23 by the aid of trace acid catalyst. Detailed experimental procedure and proposed reaction mechanism will be discussed.
- 天然有機化合物討論会の論文
- 1999-09-01
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- 80(P08) Uroporphyrinogen I octamethyl esterの異性化反応について(ポスター発表の部)