不斉二級アルコール誘導体とジクロロカルベンの立体特異的C-H挿入反応を経る不斉四級炭素の構築
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概要
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医薬品を始め、農薬、香味及び香料などには三級アルコール、α, α二置換αアミノ酸、及び4つの異なる炭素置換基を有する化合物など多くの不斉四級炭含有化合物が知られている。従って、光学的に純粋な不斉四級炭素合成素子はそれらの生物活性化合物の合成にとって重要な原料となる。不斉三級アルコールとは異なり、不斉二級アルコールは直接天然からも、また、化学的並びに生物学的方法での不斉合成によっても比較的容易に調達できるようになってきている。著者らは相間移動触媒の存在下、CHCl_3と50%NaOHから発生させたジクロロカルベンの挿入反応と引き続く脱保護を経由する、保護された不斉二級アルコールから不斉三級ジクロロメチルカルビノール体への立体特異的変換法を開発した。得られるカルビノール体は塩基処理により中間体αクロロエポキシド体に変換され、引き続くNaN_3及びKCNとの反応によりそれぞれαアジドアルデヒド及びαシアノアルデビド体へ誘導できる。この変換の中で、非ベンジル型基質ではエポキシド環のS_N2型開環反応が進行し絶対配置の反転した生成物が得られる。一方、ベンジル型αクロロエポキシド体は極めて不安定で、直ちに不斉反転を伴ってαクロロエポキシド体へ異性化し、引き続くアジド化、シアノ化反応により出発原料である不斉三級ジクロロメチルカルビノール体の不斉が保持されたαアジドアルデヒド及びαシアノアルデビド体がそれぞれ得られる。非ベンジル型不斉三級ジクロロメチルカルビノール体をMeOH中、長時間K_2C0_3で処理すると不斉中心が反転したαメトキシアルデヒド体が得られるが、ベンジル型基質では同様の処理でαクロロアルデヒド体を経由し、完全な立体保持様式でαヒドロキシアルデビドジメチルアセタール体が得られる。この度開発した方法は新規且つ簡便な不斉四級炭素合成素子の構築法を提供するものである。一つの適用例として、(R)-O,O-イソプロピリデングリセノレアルデビドから誘導された不斉三級ジクロロメチルカルビノール体を活用し、抗真菌δラクトンである(R)-(+)-タニコライドの合成を行った。
- 2005-06-30
著者
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正木 幸雄
Gifu Pharmaceutical University
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正木 幸雄
岐阜薬科大学:(現)名城大学薬学部薬化学教室
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正木 幸雄
岐阜薬科大学
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正木 幸雄
岐阜薬科大学合成薬品製造学教室
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