Synthesis and use of borane and platinum(II) complexes of 3‐diphenylphosphino‐1‐ phenylphospholane (LuPhos)

Abstract

ABSTRACT:

Environmentally Friendly Chemistry with Organophosphorus Syntheses in Focus

“…The relative position of the two P(III)-functions was confirmed by 31 P NMR spectral data and quantum chemical calculations [65,[84][85][86][87][88]. It is noteworthy, that the platinum complex of the 3-diphenylphosphino-1-phenyl-1,2,3,6-tetrahidrophosphinine (36*) was also prepared in an optically active form [65].…”

“…The platinum complexes of the mono-or bidentate P-heterocylic ligands (28, 32b-c, 34, 36, 38, 41c-d and 41f-g) were tested as catalysts in the hydroformylation of styrene (Scheme 18) [34,66,73,82,84,90]. The selectivity of the catalyst is important, as In most of the cases, an unusual preference for the branched aldehyde was observed that makes our Pt-complexes valuable.…”

3‐P⩵O‐Functionalized Phospholane 1‐Oxides by the Michael Reaction of 1‐Phenyl‐2‐phospholene 1‐Oxide and Dialkyl Phosphites, H‐Phosphinates, or Diphenylphosphine Oxide

“…The 3-phosphono products as 2a and 2b were obtained as a 1:1 mixture of two diastereomers. This approach gives the adduct as a single isomer [23]. The use of 6H-dibenzo[c,e][1,2]oxaphosphorine 6-oxide as the reagent at 180 • C for 1 h gave product 2e in a conversion of 93% as a 56-31-10-3% mixture of four isomers (Table 1, entry 7).…”

“…In these cases, the reagent with P(O)H function was converted to the corresponding anion by a reaction with trimethylaluminum prior to the addition [14][15][16]. Analogously, double deoxygenation of 3-phosphinoxido-1-phenylphospholane 1-oxide provided the bidentate P-ligand LuPhos [22] whose complexation furnished the corresponding five-ring platinum complex [23]. The resulting 3-P O-functionalized-1,2,3,6tetrahydrophosphinine oxides [14][15][16][17] and the corresponding 1,2,3,4,5,6-hexahydrophosphinine oxides (obtained by catalytic hydrogenation of the tetrahydro derivatives) [18,19] are valuable species, especially the 3-diphenylphosphinoxido-1-phenyl derivatives, as after double deoxygenation and complexation of the bidentate P-ligands so obtained with dichlorodibenzonitrile platinum, cis-chelate Ptcomplexes may be obtained from them [20,21].…”

Application of Microwave Irradiation in the Synthesis of P-Heterocycles

“…In connection with the synthesis of the precursor of LuPhos and its Pt complex [59], the addition of diphenylphosphine oxide to 1-phenyl-2-phospholene 1-oxide (40) was studied under MW conditions. In connection with the synthesis of the precursor of LuPhos and its Pt complex [59], the addition of diphenylphosphine oxide to 1-phenyl-2-phospholene 1-oxide (40) was studied under MW conditions.…”