Chiral arene ruthenium complexes: Part 3. [Ruthenium(η 6-arene)(η 4-1,5-cyclooctadiene)] complexes with N or O donor functions in the arene side chain

Abstract

Arene ruthenium(0) complexes with carbonyl side chain functionalities like [Ru(η 6-C 6H 5COR)(η 4-COD)] or [Ru(η 6- o-C 6H 4{R 1}COR)(η 4-COD)] (COD=1,5-cyclooctadiene; R=H, CH 3; R 1=H, CH 3, OCH 3) are easily accessible by replacing the naphthalene ligand of [Ru(η 6-naphthalene)(η 4-COD)] ( 1) through an arene exchange reaction. These carbonyl species are susceptible to standard organic reactions of the carbonyl function, thus allowing the introduction of dangling side chains bearing highly polar functions like hydroxyl or amino groups. Aldol reaction of [Ru( o-C 6H 4{CH 3}COCH 3)(COD)] ( 3) with (−)-menthylchloroformate in the presence of LDA (LDA=lithium diisopropylamide) leads to a diastereomeric mixture of [Ru(menthyl-{3-oxo-3-η 6- o-tolyl}propionate)(COD)] ( 10). However, treatment of 3 with LDA and o-tolylaldehyde or benzaldehyde affords the unexpected products [Ru(1-η 6- o-tolyl-3- o-tolylpropan-1-one)(COD)] ( 11) and [Ru(1-η 6- o-tolyl-1-phenylpropan-1-one)(COD)] ( 12). A diastereoselective addition (88% de) of deprotonated menthylacetate to [Ru( o-tolylaldehyde)(COD)] ( 4) results in the formation of [Ru(menthyl 3-η 6- o-tolyl-3-hydroxypropionate)(COD)] ( 13). Racemic planar-chiral aldehyde complexes 2 and 4 react with amines giving the imination products in good yield. In case of reaction between 2 and ( R)- N-amino-2-(methoxymethyl)-pyrrolidine (RAMP), diastereomeric [Ru( N-[[η 6-(2-methylphenyl]methylene]-( R)-2-(methoxymethyl)-1-pyrrolidinamine)(COD)] ( 17) is formed. The diastereomers ( R,R)- 17 and ( S,R)- 17 have been separated by fractional crystallisation. Asymmetric arene ruthenium complexes with a defined planar-chiral configuration are thus accessible. Reduction of [Ru(3-η 6-phenyl-( R)-methylbutyrate)(COD)] ( 7) with LiAlH 4 yields the chiral γ-alcohol [Ru(3-η 6-phenyl-( R)-1-butanol)(COD)] ( 18). A Wittig olefination converts the aldehyde complex 4 into a mixture of E- and Z-isomeric [Ru(1-η 6- o-tolyl-2-phenylethylene)(COD)] 21a and 21b, which were separated again by fractional crystallisation.