of main observation and conclusion A new class of axially chiral aryl-alkene-indole frameworks have been designed, and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic (Z/E)-selective and enantioselective (4+3) cyclization of 3-alkynyl-2-indolylmethanols with 2-naphthols or phenols (all >95 : 5 E/Z, up to 98% yield, 97% ee). This reaction also represents the first catalytic asymmetric construction of axially chiral alkene-heteroaryl scaffolds, which will add a new member to the atropisomeric family. This approach has not only confronted the great challenges in constructing axially chiral alkene-heteroaryl scaffolds but also provided a powerful strategy for the enantioselective construction of axially chiral aryl-alkene-indole frameworks.

The first enantioselective construction of a new class of axially chiral naphthyl‐indole skeletons has been established by organocatalytic asymmetric coupling reactions of 2‐naphthols with 2‐indolylmethanols (up to 99 % yield, 97:3 e.r.). This approach not only affords a new type of axially chiral heterobiaryl backbone, but also provides a new catalytic enantioselective strategy for constructing axially chiral biaryl scaffolds by making use of the C3‐electrophilicity of 2‐indolylmethanols.

The first organocatalytic asymmetric inverse-electron-demand 1,3-dipolar cycloaddition of the title imines (I) is described. Chiral bicyclic pyrazolidin-3-one derivatives (III) (18 example) are thus obtained in excellent diastereoselectivity and good enantioselectivity. -(ZHU, R.-Y.; WANG, C.-S.; ZHENG, J.; SHI*, F.; TU, S.-J.; J. Org. Chem. 79 (2014) 19, 9305-9312, http://dx.doi.org/10.1021/jo5018469 ; Sch. Chem. Chem. Eng., Jiangsu Norm. Univ., Jiangsu, Xuzhou 221116, Peop. Rep. China; Eng.) -R. Staver 13-197

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Framework. -For the first time the enantioselective cycloaddition of isatin-derived 3-indolylmethanol is presented realized by an unprecedented formal [3 + 3] cycloaddition of azomethine ylide instead of the common [3 + 2] cycloaddition. -(SHI, F.; ZHU, R.-Y.; DAI, W.; WANG, C.-S.; TU*, S.-J.; Chem. -Eur. J. 20 (2014) 9, 2597-2604, http://dx.