Diastereoselective oxidative addition of cyclic thiosulfinates to platinum(0) compounds:: chiral platinum(II) complexes with sulfenato ligands -: Crystal structures of S(O)-CH2-CH(OAc)-CH(OAc)-CH2-S and dppePt[S(O)-(CH2)4-S] Part 16.: Metal complexes of functionalized sulfur-containing ligands

The oxidative addition reactions of the racemic thiosulfinates S-(CH2)(4)-S(O) (1) and S-CH2-(C6H4)-CH2- S(O) (4) with dppePt(eta (2)-C2H4) (6) led to the 1-sulfenato-4-thiolato platinum(II) complexes dppePt[S(O)-(CH2)(4)-S] (8) and dppePt[S(O)-CH2 (C6H4)-CH2-S] (9): the crystal structure of complex 8 was determined. The oxidative addition of the racemic thiosulfinate (S-CH2-CH(OAc)-CH(OAc)-CH2-SO) [(R*(SO), R*, R*)-2] to (Ph3P)(2)Pt(eta (2)-C2H4) (5) gave two diastereoisomers of compound (Ph3P)(2)Pt[S(O)-CH2-CH(OAc)-CH(OAc)-CH2-S] (10) in a ratio 1:1. The thiosulfinates [(R*(SO), R*, R*,)-2] and [(R*(SO), R*, S*)-3] reacted with [(R, R -diop)]Pt(eta (2)-C2H4) (7) to yield four diastereoisomers each of the complexes [(R,R -diop)]Pt[S(O)-CH2 CH(OAc)-CH(OAc)-CH2-S] (11) and 12 in a ratio 100:100:1:1 and 10:10:1:1, respectively. [(R*(SO), R*, S*)3] was characterized structurally. Treatment of the mixture of diastereoisomers of complex 11 with two equivalents of dppe gave only one diastereoisomers of complex dppePt[S(O)-CH2- CH(OAc)-CH(OAc)-CH2-S] (13). (C) 2001 Elsevier Science B.V. All rights reserved.