No abstract

A reaction pairing strategy centered on utilization of a reaction triad (sulfonylation, SNAr addition and Mitsunobu alkylation) generating skeletally diverse benzofused tricyclic and bicyclic sultams is reported. Pairing sulfonylation and SNAr reactions yields bridged, tricyclic and bicyclic benzofused sultams. Application of the Mitsunobu reaction in a sulfonylation–Mitsunobu–SNAr pairing allows access to benzo-oxathiazocine-1,1-dioxides, while a simple change in the order of pairing to sulfonylation–SNAr–Mitsunobu affords structurally different, benzofused bridged tricyclic sultams.

Scandium triflate is an effective pre-catalyst for the deoxygenative allylation of benzylic alcohols with a narrow substrate window. The reaction is shown to proceed through a "hidden Brønsted acid" mechanism. The reaction is efficient provided that the aryl group is neither too electron rich nor too electron poor. It is shown that this allows useful selectivity. The reaction also works for benzyhydryl alcohols with broader scope. The reaction may also be catalysed by Nafion.

The combination of norbornenyl-tagged (Nb-tagged) silica particles and functionalized Nb-tagged monomers for the generation of hybrid Si-ROMP reagents and scavengers is reported. Specifically Si-ROMP-derived bis-acid chloride, dichlorotriazine and triphenylphosphine scavenger/reagents have been grafted from the surface of silica particles utilizating surface-initiated, ring-opening metathesis polymerization (ROMP). These hybridpolymeric materials combine the physical properties of current immobilized silica reagents and represent a key advancement in load by merging the inherent tunable properties of the ROMP-derived oligomers with silica supports for application in parallel synthesis.

A synthesis of the tetrahydropyran (THP) moiety of bistramide D has been completed by using cross‐metathesis and kinetically controlled intramolecular oxa‐Michael addition to form the ring with excellent trans selectivity. The C9 methyl substituent was introduced by using an unsaturated sulfone building block, which can be most effectively prepared through a combination of diastereoselective allylation and alkene isomerisation. The effect of this methyl group on subsequent cross‐metathesis reactions can be mitigated by careful choice of reaction conditions.