CHIRAL ECONOMIC SYNTHESIS OF (R)-MUSCONE AND (S)-MUSCONE USING CYCLOFRAGMENTATION OF EPOXYSULFONES
CHIRAL ECONOMIC SYNTHESIS OF (R)-MUSCONE AND (S)-MUSCONE USING CYCLOFRAGMENTATION OF EPOXYSULFONES
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DOI：
10.1002/hlca.19770600323
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发表时间：
1977-01-01
影响因子：
1.8
通讯作者：
FISCHLI, A
中科院分区：
文献类型：
--
作者：
BRANCA, Q;FISCHLI, A
从异丁酸（2）开始，使用恶臭假单胞菌（S）-β-进行微生物氧化，制备了羟基异丁酸（3）。由该假对称中间体通过改变反应顺序合成了2种对映体溴代衍生物8（R）和20（S）。由2种溴化合物8和20和环十二酮1开始的格氏反应在氢解后产生2种对映体二醇9和21（1 + 8 → 21）。9，1 + 20 →21)参见随后的转化产生2种对映异构烯烃衍生物12和24。用过酸氧化12产生2种环氧砜13和14的混合物。将烯烃衍生物24氧化成25和26的相应混合物。1锅环化断裂产生（E）-和（Z）-3-甲基环十五碳-4-烯-1-酮（13 + 14-）的混合物。15 + 16，25 + 26 →27 + 28）。最终氢化产生天然（R）-和非天然（S）-麝香酮（3-甲基环十五烷酮）。将原始起始材料转化为所需的光学活性目标产物，而不损失具有不期望的绝对构型的材料。用手性经济合成的概念来描述具有上述特征的合成序列。
Starting with isobutyric acid (2) and using a microbiological oxidation with Pseudomonas putida (S)-.beta.-hydroxy-iso-butyric acid (3) was prepared. From this pseudosymmetrical intermediate the 2 enantiomeric bromo derivatives 8 (R) and 20 (S) were synthesized by altering the sequence of the reactions. A Grignard reaction starting from the 2 bromo compounds 8 and 20 and from cyclododecanone 1 produced after hydrogenolysis the 2 enantiomeric dialcohols 9 and 21 (1 + 8 .fwdarw. 9, 1 + 20 .fwdarw. 21) cf. The subsequent transformations led to the 2 enantiomeric olefin derivatives 12 and 24. Oxidation of 12 with peracid produced a mixture of the 2 epoxy-sulfones 13 and 14. The olefin-derivative 24 was oxidized to the corresponding mixture of 25 and 26. A 1 pot cyclofragmentation produced a mixture of (E)- and (Z)-3-methylcyclopentadec-4-en-1-one (13 + 14 .fwdarw. 15 + 16, 25 + 26 .fwdarw. 27 + 28). The final hydrogenation led to natural (R)- and unnatural (S)-muscone (3-methylcyclopentadecanone). The archiral starting material was transformed to the desired optically active target products without loss of material with undesired absolute configuration. The notion of chiral economic synthesis was used to characterize synthetic sequences with the above-mentioned features.