Monoprotection of Diamondoid Diols
Monoprotection of Diamondoid Diols
复制标题
金刚石二醇的单保护
DOI：
10.1055/s-0028-1087305
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发表时间：
2008
期刊：
影响因子：
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通讯作者：
Peter R. Schreiner
中科院分区：
文献类型：
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作者：
Hartmut Schwertfeger;Christian Würtele;Michael Serafin;Heike Hausmann;Robert M. K. Carlson;Jeremy E. P. Dahl;Peter R. Schreiner
意义：作者描述了一种选择性保护对称类金刚石二醇的方法，从而能够合成不对称类金刚石衍生物。作者首先将单保护二醇 1 作为三氟乙醇 (TFE) 醚，收率良好。接下来，他们利用里特反应将未保护的醇转化为以酰胺形式保护的胺。将 TFE 醚保护的醇交换为三氟乙酸酯保护的醇，然后水解，得到 6. Koch-Haaf 反应，然后进行酯化、纯化和随后的水解，得到双官能氨基酸 8. 评论：可以从石油中分离出各种形状和大小的金刚石。金刚石类化合物是刚性的，不含双键或三键，并且在 X 射线照射时显示出负电子亲和力。它们固有的对称性代表了以有效和受控方式制备二取代衍生物的挑战。所述方法的成功部分归因于金刚烷二醇在 TFE 中的溶解度。它通常用于类金刚石以及苄基和乙炔基二醇的单保护。
Significance: The authors describe a method of selective protection of symmetric diamondoid diols enabling the synthesis of unsymmetrical diamondoid derivatives. The authors first monoprotect diol 1 as a trifluoroethanol (TFE) ether in good yield. Next they convert the unprotected alcohol into an amine protected as an amide using the Ritter reaction. Exchange of the TFE ether protected alcohol to the trifluoroacetate-protected alcohol, followed by hydrolysis yields 6. A Koch–Haaf reaction followed by esterification, purification, and subsequent hydrolysis yields difunctional amino acid 8.Comment: Diamondoids of various shapes and sizes can be isolated from petroleum. Diamondoids are rigid without containing double or triple bonds, and display a negative electron affinity when irradiated with X-rays. Their inherent symmetry represents a challenge in the preparation of disubstituted derivatives in an efficient and controlled manner. The method described succeeds in part due to the solubility of diamondoid diols in TFE. It is general for the monoprotection of diamondoid, as well as benzylic and ethynyl diols.