芳烴的無金屬直接乙?氧基化和從(+)?脫氫樅胺全合成17?羥基曼陀羅B;Metal?Free, Direct Acetoxylation of Arenes and Total synthesis of 17?Hydroxymandarone B from (+)?Dehydroabietylamine

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/85819

Title:	芳烴的無金屬直接乙?氧基化和從(+)?脫氫樅胺全合成17?羥基曼陀羅B;Metal?Free, Direct Acetoxylation of Arenes and Total synthesis of 17?Hydroxymandarone B from (+)?Dehydroabietylamine
Authors:	阮氏英虹;HONG, NGUYEN THI ANH
Contributors:	化學學系
Keywords:	直接乙?氧基化;17?羥基曼陀羅 B;Direct Acetoxylation;17?Hydroxymandarone B
Date:	2021-08-27
Issue Date:	2021-12-07 11:29:58 (UTC+8)
Publisher:	國立中央大學
Abstract:	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. ?
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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