芳烴的乙?氧基化是重要的反應,也是化學中未滿足的需求。 我們報告了在三氟乙酸、乙酸和乙酸酐的無水環境下使用硝酸鹽進行的無金屬直接乙?氧基化反應。 芳烴(31 個實例)的氧化電位(Eox,單位為 V vs SCE)低於苯(2.48 V),以良好的產率和區域選擇性被乙?氧基化。我們 提出了一種逐步的單電子轉移機制。
樅烷二? (±)?17?Hydroxymandarone B (3) 的首次具有生物學意義的合成是從 (+)?脫氫樅胺實現的。 乙?氧基化是簡單合成單乙酸酯 (7)、二乙酸酯 (4) 和三乙酸酯 (5) 的重要步驟。 這些化合物是 (±)?17?Hydroxymandarone B (3) 合成中的關鍵中間體。 在這個關鍵程序之後,精心控制的最終程序被開發出來,導致天然物的完成。 ;Acetoxylation of arenes is important reaction and an unmet need in chemistry. We report a metal?free, direct acetoxylation reaction using nitrate under an anhydrous environment of trifluoroacetic acid, acetic acid and acetic anhydride. Arenes (31 examples), with oxidation potentials (Eox, in V vs SCE) lower than benzene (2.48 V), were acetoxylated with good yields and regioselectivity. A stepwise, single electron?transfer mechanism is proposed.
The first biologically significant synthesis of abietane diterpene (±)?17?Hydroxymandarone B (3) was achieved from (+)?Dehydroabietylamine. Acetoxylation is an important step for the simple synthesis of monoacetate (7), diacetate (4), and triacetate (5). These compounds are key intermediates in the synthesis of (±)?17?Hydroxymandarone B (3). Following this critical sequence, a meticulously controlled final sequence of events was developed that led to the completion of the product nature. ?