A Highly Reusable Rhodium Catalyst-Organic Framework for the Intramolecular Cycloisomerization of 1,6-Enynes

The intramolecular cycloisomerization of 1,6-enynes in 95–99% ee is reported using an immobilized Rh catalyst-organic framework synthesized from alternating ring-opening metathesis polymerization (altROMP) assembly. The framework was reused up to seven times, and it was used in high turnover number (TON) batch reactions. The catalyst provided the highest TONs to date (up to 890) for the cycloisomerizations, with catalyst loadings ranging from 0.2 to 0.06 mol %.