Actuation of Asymmetric Cyclopropanation Catalysts: Reversible Single-Crystal to Single-Crystal Reduction of Metal–Organic Frameworks


  • We thank the NSF (CHE-0809776) for financial support, and Kathryn DeKrafft and Rachel Huxford for experimental help. J.M.F. is supported by a DOE Office of Science graduate fellowship under the DOE contract number DE-AC05-06OR23100. C.W. acknowledges the UNC Department of Chemistry for an Ernest L. Eliel Fellowship. S.L. is supported by a UNC William W. and Ida W. Taylor Fellowship.


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To and fro: Chiral metal–organic frameworks (CMOFs) derived from redox-active ruthenium/salen building blocks exhibited reversible single-crystal to single-crystal reduction and reoxidation. The catalytically inactive RuIII CMOFs (green; see picture) were reduced to RuII CMOFs (red) that were highly active for the asymmetric cyclopropanation of alkenes with very high diastereo- and enantioselectivities.