What Will Ferrell and Sam L. Jackson have in common: a Hollywood rant

Alright, this has nothing to do with chemistry, but it pisses me off.

I finally watched all of Iron Man today, which might be the badassiest movie to hit the silver screen in a decade. Robert Downey Jr. chats up, uppercuts, then blasts with napalm his drug-stained past one after another in this movie, then individually grabs each member of the audience and beats them senseless until they promise to remember him not for the drugs, but for being fucking awesome. Wonderful film, and a great step for Robert Downey Jr.

Unfortunately, it's like during the credits somebody took the film roll, cut it into a million pieces, threw it in a pile of manure, then tried to reconstruct it. Samuel L. Jackson makes a cameo after the credits being...OMG can you guess it...a badass. Wow. How original. Get a clue SLJ: IT GETS OLD! Let's contrast RDJ and SLJ for a second: one's professional life was nearly ruined by drug problems, and the other has been sucking the earth's tit since Pulp Fiction. One has proven his versatility, acting in such varied films as Iron Man, Charlie Bartlett, and Zodiac, while the other has resigned himself to being forgotten as a pointless character actor. The more I thought about it, Will Ferrell has unfortunately done the exact same thing: he peaked with Stranger than Fiction, and no movie of his since then has been even remotely decent. He's become not just a character actor, but a bad, stale character actor. It's sad, because both of them have so much potential. Makes me want to light a memorial bonfire with 200 copies of Snakes on a Plane and Blades of Glory.

This kind of thing seems to happen a lot. I don't blame Will Ferrell or SLJ, really. I blame Hollywood. I mean yes, it was fucking lame of SLJ to refuse to be in Star Wars III without a "badass scene" (direct quote...seriously, google it), but isn't that just a symptom of Hollywood's culture of beating what sells to death? I like the sound of that.

From me to Hollywood: stop beating what sells to death!
From me to America: stop being dumb enough to buy it!

New Blogs

Cheers to a couple of newly discovered blogs...The Chuch of the Hardwood chronicles the escapades of Berkeley natives on the basketball court, and PMGB is an awesome compendium of o-chem procedures.

Undergrad is over(grad). YES.

Chemistry that tugs at the heartstrings

Baeyer-Villiger has always been one of my favorite reactions, owing to the double coolness of the use of peracids and an alkyl migration in the mechanism. Malkov et al. have written a very nice JOC paper describing the enantioselective preparation of lactones from prochiral cyclic ketones using the Baeyer-Villiger reaction, complete with a rich history of recent chemistry in the area. They don't actually use a peracid as oxidant, opting instead for UHP (urea-hydrogen peroxide), but this slight coolness deduction is more than made up for by their use of palladium catalysis. Using chiral P,N-ligands (derived, interestingly, from terpenes), they were able to obtain up to 80% ee of chiral gamma lactones, more or less state-of-the-art for asymmetric B-V reactions. Procedures for making the ligands and even the cyclobutanone starting materials are included right there in the paper! Woohoo!

Aside: here's to hoping that when some poor grad student googles "state of the art baeyer-villiger," they end up here.

There's an odd double-slash mark next to the title of the paper, which links to a dedication to the memory of Otto Exler. I've read a lot of papers in my day, and I've honestly never seen that before. Call me sentimental, but I thought it was nice. See? Not all scientists are heartless!

For the mechanistically thirsty, this paper discusses intermediates involved in a few variants of the asymmetric B-V reaction.

And last but not least: happy end of the semester everybody!

Keeping our image strong.

Wow.

Vote for the official plaid of UK!

In other news, Evans University has just become one of three universities in the United States that doesn't exist! Can't you just feel the excitement building?

Chemistry coming soon.

Prepare for a revolution in fake flower technology, ladies

Skating Beads of Water: Chemists Reproduce the Rose's "Petal Effect"

Here's one from a genre I haven't touched yet: surface chemistry. Lin Feng et al. recently published an article in Langmuir describing the "petal effect," a surface property of rose petals that allows them to hold on to water super-tightly. The effect is apparently due to teeny little bumps and folds in the petal surface, which lead to what they call "superhydrophobicity." Of course the authors are excited for the future of nanoadhesives, et cetera...I personally just can't wait until fake flowers finally get over the hump. Imagine, a two-dollar dozen "roses"...and with those nanoadhesive petals, she'll never know the difference ;-).

Pay no attention to the data behind the SI link...

Is this not the coolest abstract photo ever? It looks like something out of Donnie Darko. The paper, an Organic Letters article from J.S. Kim et al., describes a pyrene sulfonamide with the neat little property of dimerizing and fluorescing big time in the presence of copper. The selectivity data kind of blew me away at first:That right there, ladies and gentlemen, for the non-chemists among us, at 470 nm, is an analytical chemist's wet dream. The authors did a time-resolved DFT study of the copper-containing dimer and discovered that it's an excimer, or an excited state with no global minimum of energy. Excimers "fluoresce themselves to decomposition," because they can't emit energy in the form of light and survive, since they have no minimum energy structure.

Anyway, at first glance this looks like a superb paper, aside from a couple of grammatical errors and overuse of the word "the." They make a lot of SI references in the paper, and although I don't usually read Supporting Information, I thought I'd glance at it this time since they promised pretty pictures of their computational results. What really caught my eye, however, was this figure:So much for trace analysis of water samples! Way to mention that guys! Yes, diluting the samples with a compatible solvent might work, but then you cut the concentration of copper even more, possibly pushing detection limits. Despite the omission of this teensy detail, I'd say this is worth a read.

A little bit of retrosyntheticky goodness

In celebration of being done with synthetic homework assignments, I thought I'd present this morsel of retrosynthetic tastiness:It seems so simple, doesn't it? Just a little half-inversion of stereochemistry. Just one little flip, and you're good to go. Such a teaser.

Right about when I started getting desperate, I got the idea that if there were some way to convert the syn diol back into an alkene, there was surely a way to stereoselectively make an anti diol from the alkene. Surely...heh. Googling "glycols to alkenes"--quotes and all--gives exactly three results, the first of which is a VTOC page on reactions involving sulfur and phosphorus. Thankfully that was all I needed, as the Corey-Winter reaction suited the problem quite well. The reaction involves the formation of a thiocarbonate from the two adjacent OH's and thiophosgene, followed by nucleophilic attack by trialkoxy phosphine on sulfur and the loss of S=P(OR)₃ to form a heterocyclic carbene. The carbene undergoes decarboxylation to give an alkene.

At this point I was halfway home--the only thing left was making an anti diol out of the alkene. Google came through on this one as well, yielding an OC Portal page on the Prevost reaction. I've got a soft spot in my heart for anything that involves iodine, and this one involves the utterly hardcore formation of an iodonium ion across the alkene. Benzoate anion attacks it, and benzoate's carbonyl oxygen kicks out the iodine as a leaving group from the other carbon. A second equivalent of benzoate anion comes in and displaces the newly made C-O bond, forcing the first and second benzoates into an anti relationship. Ester hydrolysis leads to the anti diol.

To quote Tim Meadows in Mean Girls: "I could not be happier this semester is ending."