The catalytic asymmetric (3 + 3) cycloaddition between different 2-indolylmethanols has been established, in which a series of chiral indole-fused six-membered heterocycles were constructed in high yields with excellent enantioselectivities. This work not only has established the first catalytic asymmetric cycloaddition between different 2-indolylmethanols but also provided a powerful strategy for constructing enantioenriched indole-fused six-membered rings. Additionally, biological evaluation discovered some products with promising antitumor activities. Notably, theoretical calculations performed on the reaction pathway and activation mode provide an in-depth understanding of this catalytic asymmetric (3 + 3) cycloaddition among different 2-indolylmethanols, which will advance the understanding of the chemistry of indolylmethanols.

建立了不同2-吲哚甲醇之间的催化不对称(3+3)环加成反应，以高产率构建了一系列具有优异对映选择性的手性吲哚稠合六元杂环。这项工作不仅建立了不同2-吲哚甲醇之间的第一个催化不对称环加成反应，而且为构建对映体富集的吲哚稠合六元环提供了强有力的策略。此外，生物学评价发现一些产品具有良好的抗肿瘤活性。值得注意的是，对反应途径和活化模式进行的理论计算提供了对不同2-吲哚甲醇之间的这种催化不对称(3 + 3)环加成反应的深入理解，这将促进对吲哚甲醇化学的理解。