Stereoselective Synthesis and Some Properties of New Chlorodiorganotin-Substituted Macrodiolides

Radical tandem addition of dialkyltin chlorohydrides, R 2 SnHCl (R = n -Bu, neophyl, Ph), to TADDOL’s substituted diacrylates ( 4 – 7 ) led to the corresponding products of cyclohydrostannation. The new optically active chlorodialkyltin-substituted 11-membered macrodiolides were obtained in very good yields and with much higher stereoselectivity than that achieved with the corresponding monohydrides, R 3 SnH. Thus, the cyclohydrostannation of diacrylate 4 and dimethacrylate 5 lead to just one diastereomer in the first case and to an easily separable mixture of two diastereomers in the second. Reduction of the new organotin macrocycles with LiAlH 4 afforded optically active organotin derivatives structurally related to glutaric acid. Oxidation of the new chlorodiorganotin-substituted macrocycles with 30% hydrogen peroxide gave the new 11-membered macrocycles 30 and 31 free of tin in an average total yield of 43.4% from TADDOL. Full 1 H, 13 C, and 119 Sn data are also reported.