Diastereoselective C-C Bond Formation by Carbene Insertions into Pt-CH3 Bonds

Iodo-methyl ligand exchange reaction in platinum complexes: A density functional study

“…Several further insertion reactions e.g. that of the carbene, formed in situ from ethyl diazoacetate, have been extensively studied with platinumalkyl complexes [5][6][7][8][9].…”

Insertion of ethyl diazoacetate into the platinum–carbon bond of Pt(diphosphine)(halide)(aryl) complexes. X-ray structure of the Pt{(2S,4S)-bdpp)}I(Ph) complex

“…Based also on the previous observations on the asymmetric carbene insertion reactions with platinum-methyl complexes [9,10], it can be predicted that in case of platinum-phenyl complexes enhanced diastereoselectivity probably needs the presence of a ligand with biaryl skeleton. Therefore, derivatives of BINAP [2,2¢-bis(diphenylphosphino)-1,1¢-binaphthyl] or BIP-HEP [2,2¢-bis(diphenylphosphino)-1,1¢-biphenyl] might provide higher diastereoselectivities.…”

“…Unlike the analogous Pt-methyl compounds, Pt(diphosphine)X(Me) [10], the starting compounds (1-8) insert ethyl diazoacetate into the Pt-aryl moiety exclusively resulting in (1a-8a). However, the insertion of :CHCOOC 2 H 5 carbene fragment took place also into the Pt-halide bond of the dihalogeno complexes Pt(diphosphine)X 2 (9)(10)(11)(12).…”

“…However, the insertion of :CHCOOC 2 H 5 carbene fragment took place also into the Pt-halide bond of the dihalogeno complexes Pt(diphosphine)X 2 (9)(10)(11)(12). The latter complexes have been formed in situ in various amounts in all cases.…”

“…In case of a chiral ligand (e.g. chiral diphosphine) diastereoselective insertion takes place [8][9][10].…”