Proline and serine derivatives undergo radical coupling to form a carbon skeleton. This process leads to a key intermediate via C-H amination cyclization. Many of these reactions occur in a single pot, enabling a single researcher to synthesize over 9 g of the intermediate in three days. The ideality is 71%. This intermediate can be converted into numerous related natural products in just a few steps. This is truly impressive work by Professor Baran.
Additionally, the first synthesis of neo-STX has been achieved. Although the final route is short, it appears to be the result of considerable effort, such as timing the nitrogen oxidation and protecting the hydroxylamine.
The practical synthesis of the starting material, 4-hydroxyproline, is also significant. Genetically modifying a promising oxidase increased the yield from proline to 61%.
This is truly hybrid natural product synthesis, incorporating radical reactions, late-stage oxidation, and biological methods.
Saxitoxin and related natural products uploaded.
https://www.ohira-sum.com/wp-content/uploads/2025/11/nat25-646-351.pdf
プロリンとセリンの誘導体をラジカルカップリングさせて炭素骨格をつくり，C-Hアミノ化環化で多くのSTXに変換できる重要中間体に導きます。多くの反応がワンポットで行われ，一人で３日間に９ｇ以上合成できたとのこと。アイデアリティ71% 。多くの関連天然物がここから数段階で合成できます。さすがBaran先生。
加えてネオSTXの初合成も達成しています。最終的には短工程ですが，窒素の酸化のタイミングとかヒドロキシルアミンの保護とか相当な苦労の結果のようです。
原料となる4-ヒドロキシルプロリンの実用的合成も重要で，有望な酸化酵素を改変して，プロリンからの収率を61％まで上げています。
ラジカル反応，後期酸化，生物的手法とまさにハイブリッド天然物合成です。
Proline and serine derivatives undergo radical coupling to form a carbon skeleton. This process leads to a key intermediate via C-H amination cyclization. Many of these reactions occur in a single pot, enabling a single researcher to synthesize over 9 g of the intermediate in three days. The ideality is 71%. This intermediate can be converted into numerous related natural products in just a few steps. This is truly impressive work by Professor Baran.
Additionally, the first synthesis of neo-STX has been achieved. Although the final route is short, it appears to be the result of considerable effort, such as timing the nitrogen oxidation and protecting the hydroxylamine.
The practical synthesis of the starting material, 4-hydroxyproline, is also significant. Genetically modifying a promising oxidase increased the yield from proline to 61%.
This is truly hybrid natural product synthesis, incorporating radical reactions, late-stage oxidation, and biological methods.