This work describes developments of i) a catalytic asymmetric protonation reaction of ketene dithioacetals
using a chiral Brønsted acid as a catalyst and ii) a heterogeneous catalysis using textiles as solid support
materials. First, for an asymmetric protonation reaction of ketene dithioacetals, we have disclosed a facile
preparation of various lactones and hydrocoumarins. The formation and application of ketene dithioacetals
was well demonstrated and fully chracterized. The key enantiodetermining step, an asymmetric protonation
reaction, was smoothly catalyzed by BINOL‐based Brønsted acids. The desired dithioacetal protected
hydrocoumarins were obtained in good yields and high enantioselectivities. The utility of the obtained
enantioenriched products were further demonstrated by synthesizing a natural product and conducting a large
scale reaction. Secondly, we have successfully demonstrated a facile preparation of textile‐immobilized
heterogeneous catalysts. As a general method, photochemical reaction conditions can provide diverse solidsupported
organocatalysts within one‐step from inexpensive starting materials. Further applications and
mechanistic studies revealed the high efficiency and application potential of the presented methodology
