顺式对薄荷-8-烯-1,7-二醇、顺式对薄荷烷-1,7-二醇和顺式对薄荷烷-1,7,8-三醇的立体选择性合成。
Stereoselective synthesis of cis-p-menth-8-ene-1,7-diol, cis-p-menthane-1,7-diol, and cis-p-menthane-1,7,8-triol.
作者信息
Kobler Christoph, Effenberger Franz
机构信息
Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany.
出版信息
Chemistry. 2005 Apr 22;11(9):2783-7. doi: 10.1002/chem.200401147.
The natural products cis-p-menthane-1,7-diol (cis-IV), cis-p-menth-8-ene-1,7-diol (cis-I) and cis-p-menthane-1,7,8-triol (cis-II) are obtained starting from the corresponding cis-cyanohydrins, cis-2 and cis-7, respectively, by chemical transformation of the cyano into the hydroxymethyl group. The key step of the synthesis is the very high cis-selectivity (> or = 96 %) of the MeHNL-catalyzed HCN addition to 4-alkylcyclohexanones. From 4-isopropylcyclohexanone (1) the cyanohydrin cis-2 and from 4-(1-methylvinyl)cyclohexanone (6) the cyanohydrin cis-7 result almost quantitatively. Regioselective hydroxylation of cis-I affords the triol cis-II. X-ray crystal structure determinations of the final products confirm their cis-configuration.
天然产物顺式对薄荷烷-1,7-二醇（顺式-IV）、顺式对薄荷-8-烯-1,7-二醇（顺式-I）和顺式对薄荷烷-1,7,8-三醇（顺式-II）分别从相应的顺式氰醇顺式-2和顺式-7出发，通过将氰基化学转化为羟甲基而得到。合成的关键步骤是MeHNL催化HCN加成到4-烷基环己酮时具有非常高的顺式选择性（≥96%）。从4-异丙基环己酮（1）几乎定量地得到氰醇顺式-2，从4-(1-甲基乙烯基)环己酮（6）几乎定量地得到氰醇顺式-7。顺式-I的区域选择性羟基化得到三醇顺式-II。最终产物的X射线晶体结构测定证实了它们的顺式构型。
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