STUDIES ON THE SYNTHESIS OF APHIDICOLIN - THE DIELS-ALDER ROUTE TO SPIROCYCLIC INTERMEDIATES
STUDIES ON THE SYNTHESIS OF APHIDICOLIN - THE DIELS-ALDER ROUTE TO SPIROCYCLIC INTERMEDIATES
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DOI：
10.1039/p19860001507
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发表时间：
1986-08-01
期刊：
影响因子：
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通讯作者：
RAPHAEL, RA
中科院分区：
文献类型：
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作者：
BELL, VL;HOLMES, AB;RAPHAEL, RA
亚环己基丙二酸异丙酯（6; R1 = R2 = H; R1，R2 = OCH 2CH 2 O;和R1，R2 = SCH 2CH 2S）与丁二烯、2-三甲基甲硅氧基丁-1，3-二烯和3-三甲基甲硅氧基戊-2，4-二烯进行环加成，得到相应的螺环加合物（7; R1 = R2 = H），（11; R1，R2 = OCH2CH2O; R1，R2 = SCH2CH2S），和（23; R1，R2 = OCH2CH2O; R1，R2 = SCH2CH2S）。三甲基硅烯醇醚（十一、R1，R2 = SCH 2CH 2S）通过化合物（12），（14），（15），（16），和（17）与甲苯-对-磺酸盐（18）反应，后者进行碱催化的分子内烯醇化物烷基化反应，得到双环[3.2.1]辛酮（19）和（20），它们作为蚜虫菌素（1）和斯替莫定（2）的模型化合物。合成.加合物（23; R1，R2 = SCH 2CH 2S）通过三酮（25）转化为酯（27），其烯醇醚衍生物（28）是关键的蚜虫菌素中间体（4）的有希望的前体。
The isopropylidene cyclohexylidenemalonates (6; R1 = R2 = H; R1, R2 = OCH2CH2O; and R1, R2 = SCH2CH2S) undergo cycloaddition with butadiene, 2-trimethylsilyloxybuta-1,3-diene, and 3-trimethylsilyloxypenta-2,4-diene to give the corresponding spirocyclic adducts (7; R1 = R2 = H), (11; R1, R2 = OCH2CH2O; R1, R2 = SCH2CH2S), and (23; R1, R2 = OCH2CH2O; R1, R2 = SCH2CH2S). The trimethylsilylenol ether (11; R1, R2 = SCH2CH2S) was converted via compounds (12), (14), (15), (16), and (17) to the toluene-p-sulphonate (18) which undergoes base-catalysed intramolecular enolate alkylation to give the bicyclo[3.2.1]octanones (19) and (20) which serve as models for aphidicolin (1) and stemodine (2) synthesis. The adduct (23; R1, R2 = SCH2CH2S) was converted via the trione (25) into the ester (27) whose enol ether derivative (28) is a promising precursor to the key aphidicolin intermediate (4).