Friday Fun: RCDEYM

Readers: Do you recognize that acronym?

Hint: It's a reaction related to RCM, with a taxane twist...

I've seen some strange nicknames in the organic literature, but this one takes the cake. How do you even pronounce it* in casual conversation? Is muttering "R-C-D-E-Y-M" actually more efficient than saying its real name?

Ye Gods.

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* "Racadaim?"

If you're truly stumped, click here or here for an answer. 

Stump Your Friends! A Devious Diels-Alder

You may have noticed a lot of chatter about the "turbo-charged" Diels-Alder (Chemistry World, C&EN) recently reported by Prof. Thomas Hoye and colleagues at UMN. With all the fuss, another equally exciting, albeit subtler D-A development might have been overlooked.

Introducing: the metathesis-modified Himbert reaction!

Wait...the what?

Browse on over to Org. Lett. ASAP for a crazy two-stepper you're sure to love. Here's the opening scheme, so sharpen those pencils, and try some electron-pushing before I tell you the secret:

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Give up? I tried all sorts of pi-arene cyclizations, and drew out amide tautomers until my eyes bled. But the real answer, clues author Prof. Chris Vanderwal, lies 30 years in the past. A brief (2/3 page!) 1982 communication in ACIEE related a rare bird indeed: an unactivated benzene ring participating as a diene, with no added metal catalysts, pressure, acids, or bases. Upon heating, the tethered alkyne isomerizes to an allenamide, which gladly serves as the dienophile (somewhere, Richard Hsung is smiling).

Source: Himbert, Henn ACIEE 1982, p. 620

Vanderwal's insight comes next: seeing a strained [2.2.2] diene, he figures he can pop it open with some metathesis magic. A touch of Hoveyda-Grubbs, some ethylene, and a little heat rearrange the strained system to a complex 7-6-5 tricyclic lactam. His group prepares quite a few of these scaffolds, and hopes to utilize them to access several of the Erythrina alkaloids. 

P.S. First one to use this problem for 'mechanisms' group meeting wins!

Chemistry Bumper Cars - Bertrand Edition

A little birdie has written to tell me of another fairly high-profile move - Prof. Guy Bertrand, formerly of UC-Riverside, seems to have moved to UC-San Diego* as early as June 2012.

Not familiar? His research covers main group complexes of phosphorus and boron, metathesis, gold catalysis, and some really neat takes on the N-heterocyclic carbene ligand framework (P.S. It certainly doesn't hurt when you're averaging a Science paper every other year!)

No word on whether the move was precipitated in order to fill a "Nicolaou-sized" hole in the UCSD faculty...

Congrats, Prof. Bertrand! We'll add you to the new map next year.

*I may be the only one entertained by this, but Prof. Bertrand is listed in the UC-San Diego "new faculty" page as "Professor, Above Scale (Distinguished)." Which begs the question, UCSD - show me that scale!