om9b00610_si_001.pdf (1.53 MB)
Probing the Hydrogenation of Vinyl Sulfoxides Using para-Hydrogen
journal contribution
posted on 2019-11-14, 20:47 authored by Ben J. Tickner, Rachel R. Parker, Adrian C. Whitwood, Simon B. DuckettVinyl sulfoxides are an important functional group used
in a wide range of organic transformations. Here, we use [IrCl(COD)(IMes)]
where IMes = 1,3-bis(2,4,6-trimethyl-phenyl)imidazole-2-ylidene and
COD = cis,cis-1,5-cyclooctadiene
to rapidly hydrogenate phenylvinylsulfoxide. We use para-hydrogen-induced hyperpolarization (PHIP) to follow this reaction
with [IrCl(H)2(IMes)(S(O)(Ph)(Et))2] dominating
in the later stages. Decomposition to form the reduced C–S
bond cleavage product [Ir2(H)3(κ2-H)(κ2-SPh)2(IMes)2(S(Et)(Ph)O)]
limits turnover. The related product [Ir2(H)4(κ2-S)(IMes)2(S(O)(CH2Ph)2)2] is formed from dibenzylsulfoxide, demonstrating
the wider utility of this transformation.
