環状イミン類の新しい不斉還元剤 : 不斉水素化トリアシルオキシホウ素ナトリウム
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概要
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Asymmetric reduction of prochiral cyclic imines with chiral sodium acyloxyborohydrides (5 a-i), which are easily prepared by the reaction of NaBH<SUB>4</SUB> with various <I>N</I>-acyl α-amino acids, has been investigated. Of these new reducing agents, triacyloxyborohydrides (5 c-f), derived from NaBH<SUB>4</SUB> (1 eq.) and (<I>S</I>)-<I>N</I>-acylproline (3 eq.), were found to reduce 3, 4-dihydropapaverine (1) in tetrahydrofuran to (<I>S</I>)-norlaudanosine (2) in 60 % optical yield. The <I>N</I>-benzyloxycarbonyl derivative (5 c) could be isolated as a powder and characterized. The effect of solvents on this asymmetric reduction has been examined by the use of the isolated reagent (5 c) halogenated alkane solvents such as CH<SUB>2</SUB>Cl<SUB>2</SUB> or CHCl<SUB>2</SUB>CH<SUB>3</SUB> gave a better optical yield of compound (2) (70 % e. e.). The reagent (5 c); also reduced other cyclic imines (6 a-c) and (8) to the corresponding alkaloids (7 a-c) and (9) in excellent optical yields (70-86 % e. e.), providing an effective route to the asymmetric synthesis of these alkaloids. The asymmetric reduction of the imines (10 and 13) also proceeded smoothly to furnish the compounds (11 and 14), the precursors of TMQ and TA-073 (bronchodilating agents), in high optical yields. A possible reaction path for this reduction is also presented.
- 社団法人 有機合成化学協会の論文
著者
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山田 幸一郎
Organic Chemistry Research Laboratory Tanabe Seiyaku Co. Ltd.
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武田 幹男
Organic Chemistry Research Laboratory Tanabe Seiyaku Co. Ltd.
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武田 幹男
田辺製薬株式会社有機化学研究所
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岩隈 建男
田辺製薬 (株) 有機化学研究所
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山田 幸一郎
田辺製薬 (株) 有機化学研究所
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武田 幹男
田辺製薬 (株) 有機化学研究所
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