Department of Biochemistry, The University of Texas Southwestern Medical Center at Dallas , 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, United States.
J Am Chem Soc. 2013 Nov 6;135(44):16380-3. doi: 10.1021/ja4095473. Epub 2013 Oct 28.
Although the aromatic aza-Claisen rearrangement is a general strategy for accessing substituted aromatic amines, there are no highly enantioselective examples of this process. We report the first Brønsted acid catalyzed enantioselective indole aza-Claisen rearrangement for the synthesis of chiral 3-amino-2-substituted indoles. We present evidence for an arene CH-O interaction as a source of activation and stereoinduction, which is an unprecedented phenomenon in enantioselective Brønsted acid catalysis. The products of this reaction can be transformed into 3-aminooxindoles, which are prevalent in many biologically active small molecules.
尽管芳基氮杂-Claisen 重排是一种获得取代芳基胺的通用策略，但该过程没有高度对映选择性的例子。我们报告了首例 Brønsted 酸催化的对映选择性吲哚氮杂-Claisen 重排，用于合成手性 3-氨基-2-取代吲哚。我们提供了证据表明芳基 CH-O 相互作用是激活和立体诱导的来源，这在对映选择性 Brønsted 酸催化中是前所未有的现象。该反应的产物可以转化为 3-氨基氧代吲哚，它在许多具有生物活性的小分子中很常见。
