2003 Volume 123 Issue 7 Pages 577-585
The chemistry of chiral ligands for transition metal-catalyzed asymmetric reactions is an interesting research field in synthetic chemistry and has recently been the focus of much attention. Although a number of chiral ligands containing phosphorus (P) and arsenic (As) have been widely studied and are well documented, asymmetric reactions with optically active organoantimony compounds have not been reported so far. We are interested in the synthesis and utilization of optically active organoantimony compounds for asymmetric synthesis. We present here the synthesis and resolution of Sb-chiral and C2-symmetric compounds containing antimony as well as their physical and chemical properties. Resolution of (±)-1-phenyl-2-trimetylsilylstibindole (1), Sb(R/S)-(aryl) [2-(S)-(1-dimethylaminoethyl) phenyl] (p-tolyl)stibane (9), and (±)-2,2′-bis(diarylstibano)-1,1′-binaphthyl (13) can be achieved by the separation of a mixture of the diastereomeric antimony-palladium complexes. The optically pure Sb-chiral stibanes (1, 9) isolated here were optically stable, and no racemization on the chiral antimony center was observed even when they were heated under a neutral or a basic condition. Single-crystal X-ray analysis of Sb-chiral triarylstibane 9b-B revealed the presence of an intramolecular interaction between the antimony and nitrogen atoms. The optically active BINASb (13) can be used as powerful chiral ligand for the palladium-catalyzed asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propen-1-yl acetate with dimethyl malonate. We also report the synthesis, molecular structure, and fluxional behavior of the (R)-(−)-7-p-tolyldinaphtho [2, 1-b; 1′,2′-d]stibole (21c) which is the first isolated example of optically active C2-symmetric group 15 dinaphthoheteroles.
