Silane 15, easily constructed by simple methods, undergoes a cascade of radical reactions when treated with a stannane to afford the bicyclic 1,2-oxasiloles 16, with the major isomer having the ester group anti to the O-Si unit. This isomer was elaborated via 19 into 6, a deoxy derivative of the Corey lactone. In a related sequence, ketone 24 was converted into silane 35; this, too, underwent the radical cascade to afford the highly substituted 1,2-oxasiloles 36. Again the major isomer had the ester and O-Si units in an anti relationship. Elaboration of 36 (major isomer) gave the Corey lactone derivative 7. A key intermediate (32) in this second sequence was also prepared in optically pure form by starting with 2-deoxy-D-ribose. Compound 19 was converted into 8, a sequence that constitutes a formal synthesis of methyl (+/-)-epi-jasmonate. Two examples were found of selective silylation of a propargylic secondary hydroxyl in the presence of an ordinary secondary hydroxyl.

Cycloalkenyl acetylenes 4, which are easily prepared from allylic alcohols by Claisen rearrangement and homologation (1 → 4), generally undergo radical cyclization (4 → 6) on treatment with stannyl radicals. The products (6) can themselves be converted into allylic alcohols, so that the annulation sequence can then be repeated. In certain cases enyne cyclization initiated by stannyl radicals does not work, but an alternative process (cf. Scheme 9) of epoxide opening with bis(cyclopentadienyl)titanium(III) chloride can then be used. Di- and triquinanes (Scheme 3) were made by the stannyl radical approach; the epoxide route was used to prepare a simple propellane (Scheme ) and in a synthesis of (±)-ceratopicanol (Schemes and 9).

The synthesis of allylic amine libraries derived from olefin templates is described. The two-step, solution phase reaction sequence consists of amination of the template followed by Suzuki coupling and expedited purification via ion exchange chromatography. The methodology has been used to synthesize a 1344-member allylic amine library.

The preparation of molecular libraries of aminomethylbiaryls, allylic amines, and ethanolamines using solution-phase methodology is described. In particular, the use of a solid-supported base reagent (PTBD resin) and strong cation exchange(SCX) resin to effect 'catch and release' purification across these diverse libraries is highlighted.