Asymmetric Phase-Transfer-Catalyzed Intramolecular N-Alkylation of Indoles and Pyrroles: A Combined Experimental and Theoretical Investigation
Asymmetric Phase-Transfer-Catalyzed Intramolecular N-Alkylation of Indoles and Pyrroles: A Combined Experimental and Theoretical Investigation
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DOI：
10.1002/chem.201000560
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Stenta, Marco
中科院分区：
文献类型：
--
作者：
Bandini, Marco;Bottoni, Andrea;Stenta, Marco
不对称相转移催化（PTC）在过去十年中作为一种直接的合成方法用于制备对映体纯形式的手性化合物而变得突出。然而，弱非键相互作用（催化剂和基板之间），可以解释在这些过程中的立体选择性的复杂的相互作用仍然不清楚，与暂定的图形机械表示通常提出。在这里，我们提出了一个完整的帐户处理对映选择性相转移催化分子内氮杂迈克尔反应（IMAMR）的吲哚酯，作为一个有价值的合成工具，以获得附加值的化合物，如二氢吡嗪并吲哚啉酮。已经进行了计算和实验相结合的调查，以阐明这一过程的关键机制方面。
Asymmetric phase-transfer catalysis (PTC) has risen to prominence over the last decade as a straightforward synthetic methodology for the preparation of pharmacologically active compounds in enantiomerically pure form. However, the complex interplay of weak nonbonded interactions (between catalyst and substrate) that could account for the stereoselection in these processes is still unclear, with tentative pictorial mechanistic representations usually proposed. Here we present a full account dealing with the enantioselective phase-transfer-catalyzed intramolecular aza-Michael reaction (IMAMR) of indolyl esters, as a valuable synthetic tool to obtain added-value compounds, such as dihydro- pyrazinoindolinones. A combined computational and experimental investigation has been carried out to elucidate the key mechanistic aspects of this process.