Utilization of hypervalently activated organotin compounds in synthesis. Preparation and reactions of Me2N(CH2)3SnPh3

Article abstract of DOI:10.1016/0022-328X(93)80454-J

The reaction of Me2N(CH2)3SnPh3 (1) with phenol gives Me2N(CH2)3Sn(OPh)nPh(3-n) (2, n = 1; 3, n = 2) in good yields.All the phenyl groups are cleaved off when 1 is treated with glycol or pinacol, resulting in the formation of 2(OC2H4O)3 (4) and 2(OC2Me4O)3 (5), respectively.Compounds 4 and 5 are transformed almost quantitatively into Me2N(CH2)3Sn(SPh)3 (6) and H (7) by reaction with phenyl mercaptan and trimethylchlorosilane, respectively.The reaction of 2 with triethanolamine and nitrilotriacetic acid affords the newstannatrane Me2N(CH2)3Sn(OCH2CH2)3N (8) and Me2N(CH2)3Sn(OCOCH2)3N (9), respectively.However, the N-oxide derivative Me2(O)N(CH2)3Sn(OCOCH2)3N (10) is obtained by reaction of 1 with N(CH2COOH)3 in DMF.Compounds 1-10 have been characterized by means of 1H, 13C and 119Sn NMR spectroscopy and mass spectrometry.The crystal structures of Me2N(CH2)3Sn(SPh)3 (6) and Me2(O)N(CH2)3Sn(OCOCH2)3N (10) have been determined by an X-ray diffraction study.The tin atom in 6 is trigonal bipyramidal with an intramolecular Sn-N distance of 2.605(6) Angstroem.Compound 10 contains an octahedral tin with intramolecular Sn-N and Sn-ON distances of 2.231(7) and 2.101(7) Angstroem, respectively.