One-step assembly of a MacMillan catalyst-based phenolic-type polymer.

We report herein a "bottom-up" approach for the one-step assembly of a MacMillan catalyst-based phenolic-type polymer (Mac-CP). The resulting self-supported polymeric organocatalyst possesses homogeneously distributed and highly concentrated catalytic sites. Furthermore, Mac-CP is soluble in CHCN but insoluble in hexane. This unique property can be used to employ the polymer as an efficient catalyst in homogeneous organocatalysis and heterogeneous recycling. As a result, Mac-CP possesses comparable catalytic activity and enantioselectivity to its homogeneous counterpart in the asymmetric Diels-Alder reaction (95% yield, 93% enantiomeric excess (ee) for and 92% ee for ).