The Mann - Grubbs Method

A materials approach to site-isolation of Grubbs catalysts from incompatible solvents and m-chloroperoxybenzoic acid.

The development of a method for site-isolation of Grubbs second-generation catalyst from MCPBA is described. In these reactions, Grubbs catalyst was dissolved in a solvent consisting of a mixture (1:1 v/v) of 1-butyl-3-methylimidazolium hexafluorophosphate and methylene chloride and completely encapsulated within a thimble fabricated from polydimethylsiloxane (PDMS). A series of molecules that ...

Solvent effects on Grubbs' pre-catalyst initiation rates.

Initiation rates for Grubbs and Grubbs-Hoveyda second generation pre-catalysts have been measured accurately in a range of solvents. Solvatochromic fitting reveals different dependencies on key solvent parameters for the two pre-catalysts, consistent with different mechanisms by which the Grubbs and Grubbs-Hoveyda pre-catalysts initiate.

Phase Tags in the Recycling of Homogeneous Grubbs Catalysts

Since they were first synthesized in 1992, the ruthenium catalyst named after Nobel Laureate R. H. Grubbs have become a useful tool in organic synthesis. Compared to conventional heterogeneous metathesis catalysts, Grubbs catalysts are more reactive, faster to initiate and better for reaction control. Grubbs catalysts have been employed in good effort both in academia and industry, the later in...

New selectivities from old catalysts. Occlusion of Grubbs’ catalysts in PDMS to change their reactions

This article describes new selectivities for Grubbs’ first and second generation catalysts when occluded in a hydrophobic matrix of polydimethylsiloxane (PDMS). Occlusion of catalysts in mm-sized slabs of PDMS is accomplished by swelling with methylene chloride then removing the solvent under vacuum. The catalysts are homogenously dissolved in PDMS yet remain catalytically active. Many substrat...

Robert H. Grubbs - Nobel Lecture