Highly regioselective hydroformylation with hemispherical chelators

The hemispherical diphosphites (R,R)- or (S,S)-5,11,17,23-tetra-tert-butyl-25,27-di(OR)-26,28-bis(1,1'-binaphthyl-2,2'-dioxyphosphanyloxy)calix4]arene (R=OPr, OCH(2)Ph, OCH(2)-naphtyl, O-fluorenyl; R=H, R'=OPr) (L(R)), all with C(2) symmetry, have been synthesised starting from the appropriate di-O-alkylated calix4]arene precursor. In the presence of Rh(acac)(CO)(2)], these ligands straightforwardly provide chelate complexes in which the metal centre sits in a molecular pocket defined by two naphthyl planes related by the C(2) axis and the two apically situated R groups. Hydroformylation of octene with the L(Pr)/Rh system turned out to be highly regioselective, the linear-to-branched (l:b) aldehyde ratio reaching 58:1. The l:b ratio significantly increased when the propyl groups were replaced by -CH(2)Ph (l:b=80) or -CH(2)naphthyl (l:b=100) groups, that is, with substituents able to sterically interact with the apical metal sites, but without inducing an opening of the cleft nesting the catalytic centre. The trend to preferentially form the aldehyde the shape of which fits with the shape of the catalytic pocket was further confirmed in the hydroformylation of styrene, for which, in contrast to catalysis with conventional diphosphanes, the linear aldehyde was the major product (up to ca. 75 % linear aldehyde). In the hydroformylation of trans-2-octene with the L(benzyl)/Rh system, combined isomerisation/hydroformylation led to a remarkably high l:b aldehyde ratios of 25, thus showing that isomerisation is more effective than hydroformylation. Unusually large amounts of linear products were also observed with all the above diphosphites in the tandem hydroformylation/amination of styrene (l:b of ca. 3:1) as well as in the hydroformylation of allyl benzyl ether (l:b ratio up to 20).