Science Blackout Poetry

Inspired by Austin Kleon and the New York Times, honoring National Poetry Month.

Update (April 27): A Reddit commenter (rightly) points out to also assign credit to Tom Phillips' Humument Project...good call!

JACS 2012, 11992

JACS 2014, 5257

JACS 1993, 9293

Get it Funded! (A Game)

Last night, intrepid C&EN reporter Dr. Dre, err, Dr. Drahl, sent over another challenge from NOS2013:

I think Jerry Berson talked w/me re funding influencing field flux. So what's gonna happen to totsyn?
— Carmen Drahl (@carmendrahl) June 27, 2013

Let's reword that: How will changes in funding affect total synthesis, the study of assembling complex natural products from simple commercial chemicals?

Now, this isn't the first time folks have declared the synthetic field to be on death's door. Hardly. So, I answered the way I always do, which has kept the field alive and kicking long past Woodward:

@carmendrahl @2014RMC @ChemProfCramer TotSyn will survive - it'll just dress itself in new clothes for new funding opps #SameOldStory
— See Arr Oh (@SeeArrOh) June 27, 2013

Chemjobber, always one for a savvy one-liner, immediately jumped on board:

.@SeeArrOh "Towards the enantioselective nanodelivery of 56-desoxymaitotoxin" @carmendrahl @2014RMC @ChemProfCramer
— Chemjobber (@Chemjobber) June 27, 2013

Nyuk nyuk nyuk. OK, wise guy, I've got a few more, then . . .

"Reversible carbon dioxide capture using lycopodium alkaloid analogs"

"Pentacene-functionalized steroids for solar panels"

"Origin of Life: The Gliotoxin Hypothesis"

"Analysis of 10^5 novel secondary metabolites in the human gut microbiome"

OK, Readers, I'm sure you can do better. Leave me some gut-shakers and knee-slappers in the comments section!

Hi Ho, Silver! (Benzoate)

Ever feel déjà vu? You know, that feeling of having been somewhere before, or crossing a black cat twice?

Carbon dioxide - Silver benzoate "puts a ring on it"
Source: Yamada, et.al. ACIEE, 2012

I've been stalked lately by a certain catalytic reagent: silver (I) benzoate. It's everywhere! Here, Charette's using it for C-H activation, with a little dash of Pd, to produce heterocyclic drug leads. Here, Toste's group turns up the selectivity on a gold hydroamination. Just this week, Yamada and coworkers showed lactone formation via carbon dioxide fixation (see above), using a bit of pressure, some base, and...you guessed it, silver benzoate.


Makes me wonder: Did I somehow miss the signs? How long has this reagent been flying under my radar?

In 1957, the Lone Ranger
ruled the Silver Screen
Source: lonerangerfanclub.com

Quite a while, it seems. Name reaction buffs - have you heard of the Prévost? First developed in the 1930s, it produces an anti vicinal diester, forming two new C-O bonds from opposite directions on neighboring carbons. Later investigations into the "wet Prévost" reaction favored cis diols; not too shabby when you consider that the related osmium or iodonium variants were still several decades away.


In its heyday, the Prévost helped synthesize steroids, alkaloids, and polymers, and found its way into the hands of a Who's Who of the O-Chem 'golden age': Woodward, Fieser, Carothers, Winstein, Streitweiser, Gilman, Djerassi, Fries, Benkeser, Sondheimer, van Tamelen, and Witkop. Perhaps you're more of a mechanisms person? Check out this sweet ¹⁸O labeling work, courtesy of a young University of Washington chemist named Ken Wiberg (1957).

What about silver benzoate makes it so darn useful for these oxidations? First, you have a d¹⁰ late metal species, which loves to coordinate to π-bonds (alkenes, alkynes, allenes). Second, the softer nature of the resonance-stabilized benzoate might switch on different catalytic pathways, say, changing from inner- to outer-sphere. Finally, to the benzoate itself: our buddy Ken showed that it adds twice, producing a transient 5-membered, cyclic species that ultimately permits the second benzoate addition.