Rapid development in the last decade has rendered chiral organoiodine(I/III) catalysis a reliable methodology in asymmetric catalysis. However, due to the severely limited numbers of effective organoiodine catalysts, many reactions still give low to modest enantioselectivity. We report herein a solution to this issue through the introduction of a pivotal indanol scaffold to the catalyst design. Our catalyst architecture exhibits the advantage of high modularity and thereby expedites catalyst optimization. The catalyst was optimized for the challenging and highly sought-after hydrative dearomatization of 2-substituted phenols at the 4-position.

Rapid development in the last decade has rendered chiral organoiodine(I/III) catalysis ar eliable methodology in asymmetric catalysis.H owever,d ue to the severely limited numbers of effective organoiodine catalysts,m any reactions still give low to modest enantioselectivity.W er eport herein as olution to this issue through the introduction of ap ivotal indanol scaffold to the catalyst design. Our catalyst architecture exhibits the advantage of high modularity and thereby expedites catalyst optimization. The catalyst was optimized for the challenging and highly sought-after hydrative dearomatization of 2-substituted phenols at the 4-position.

Although the chemistry of frustrated Lewis pairs (FLPs) has seen tremendous developments, investigations on anionic, mono-molecular FLPs are still scarce and 1,3-zwitterions are unknown, but a functional K/OR phosphinindenoid complex can be used instead.

The molecule of the title compound, C36H60Si6, exhibits point group symmetryCi, with the centre of inversion located at the centre of the Si6ring. The Si6ring has a chair conformation. In the crystal, molecules are linkedviaC—H...π(allyl) interactions.

The cover picture shows the quantitative conversion of the substituents on a cyclic Si6 compound from allyl to methoxy groups by the reaction with methanol and catalytic amount of iodine. Dodecaallyl‐substituted Si6 compound can be easily prepared and has enough stability to the air. It has high potential as a useful precursor for a variety of functionalized Si6 compounds. In addition, an effective synthetic route to dodecachlorohexasilacyclohexane Si6Cl12 was shown. More details are discussed in the article by Yamato Omatsu, Yoshiyuki Mizuhata, and Norihiro Tokitoh on page http://onlinelibrary.wiley.com/doi/10.1002/zaac.201800171/abstract.