A few more highlights – this time from day 2 of the BOSS conference.

Masakatsu Shibasaki gave a real tour d’force, covering a hugely diverse range of reactions with an astounding array of reagents.  The Shibasaki chemical inventory must give the Corey labs a run for their money…

First-up was a bit of asymmetric epoxidation.  Shibasaki’s approach is quite different to that used by Yian Shi – rather than attempting an asymmetric oxidation, he’s targeted a asymmetric methylation of a carbonyl group, using the Corey-Chaykovsky reagent and the mother of all catalysts… (In case you’re wondering, that bad-boy weighs in at 1012 mass units)

The yields and enatioselectivities are generally excellent, but the range of substrates shown was somewhat limited – mostly aryl, but some alkyl.  This methodology nicely complements that of Shi, as the fructose based system is pretty poor when applied to terminal olefins.  Looks like Shibasaki’s running with this one though…

Next he showed us a bit of asymmetric conjugate addition of cyanide to enones.  Again, interesting catalytic system, but the group has a bit of history with this particular ligand.  In this case, the substrate screen was more extensive, showing both good yields and enantioselectivities.  However, there wasn’t much information about reactions in which R² isn’t H.

Michael Crimmins didn’t give us too much in the way of methodology – a little more on the Ti-mediated aldol he’s been developing for a few years (which is an amazingly simple reaction to do – even I managed it). He showed the extension to glycolate aldols, and their use in total synthesis with a few Laurencia targets, including laurencin itself and obtusenyn. But the show piece was his synthesis of Brevetoxin… my jaw still gapes…

More tomorrow – Hartwig and Denmark…