While I try not to operate this blog like a directory, on occasion there are links so compelling that I just have to do it.  The blog Growabrain always has great links and that was my entry point into these links. 

Apparently, someone much braver than I flew their airplane through a hole or gap in a mountain ridge. Check it out. Must be a homebuilt and must have been a calm day.  A bit of wind shear on either side of this could have ruined his/her entire day. 

In another video, a Swiss pilot flys a jet fighter through the Swiss Alps.  Pretty impressive. At about the 3 minute mark he flys up the Matterhorn.  Amazing.  This is quite skillful flying.  Any hiccup in the powerplant and you’re on the ground straight away in flaming, crumpled aluminum.

Finally, if you are not compelled to strap a single engine delta wing fighter to your backside after viewing this one, then quite possibly you are dead. Consult your physician.

Recently a colleague and I were debating the reality of a fuzzy concept referred to as “green chemistry”. Being in the specialty chemical business, as opposed to the commodity chemical business, our discussion was naturally biased to the medium batch reactor scale.  This is no trivial distinction.  Raw material consumption and side product streams from commodity continuous-process trains can be astronomical in comparison to batch reaction operations.

There was the suggestion that the whole concept was absurd and was just the latest incarnation of a tree hugging export from CA.  I’m a little bit more circumspect about it, but one thing is obvious- economics will be the driver of any green process changeover.

I’m not an expert in the green chemistry field, but some of the concepts seem clear and highly desirable.  The goal is to minimize the total chemical insult to the environment. To achieve this, a green process has to be as atom efficient as possible in the assembly of the target product, recycle solvents to the greatest extent possible, avoid all toxic metals (Pb, Hg, Cd, Cr(VI), etc., metals are forever), eliminate fugitive emissions, and probably 6 or 8 other things I can’t think of right now.

As far as I know, certain metals are already on the path to extinction as reagents in chemcial processing- mercury and lead are the obvious ones. The battery industry still uses some unfortunate metals, mostly because of the reality of the electromotive series. There are only so many electrode combinations that are feasble for commercial batteries.

One of the obvious approaches that will get us to a greener chemistry is the continued adoption of catalyzed processes. I’m not thinking about acid protons, I’m thinking of highly selective transition metal catalysts.  Synthesis chemistry is about managing reactivity through the choice of appropriate functional groups and the sequence in which they appear. The chemist has to contend with the inverse relationship of reactivity and selectivity. Catalytic reactions form reactive intermediates from otherwise docile functional groups (olefins, boronic acids, or aryl halides, for example) and bring them together into close proximity in the coordination sphere of the metal. This is a kind of tuned reactivity management that reacts functional groups that, absent the catalyst, are relatively inert. All kinds of coupling reactions come to mind- the Suzuki coupling, etc. 

Now, to be fair, to get a substrate suitably functionalized for a green transformation might require some brutish and not-so-green chemistry- preparation of specialty aryls, acetylenes, and olefins; borylation reactions; the chemistry needed to make these whizbang ligands for Pd; and, well you get the point. The final greenness has to be measured as the sum of all the green steps from some common level, if not the oil well in Kuwait itself. 

Catalysis has the benefit of allowing the activation of relatively inert functionalities for subsequent transformations. Rather than making bulk quantities of highly reactive species, a catalyst can generate it in situ and do the deed straight away.  That is certainly in the direction of green.

One of my favorite writers is Hunter S. Thompson.  His trademark acid-trip style of writing always dazzles.  Here is a piece from the Nixon years, 1973-

 “What we are looking at on all our TV sets is a man who finally, after 24 years of frenzied effort, became the President of the United States with a personal salary of $200,000 a year and an unlimited expense account including a fleet of private helicopters, jetliners, armored cars, personal mansions and estates on both coasts and control over a budget beyond the wildest dream of King Midas . . . and all the dumb bastard can show us, after five years of total freedom to do anything he wants with all this power, is a shattered national economy, disastrous defeat in a war we could have ended four years ago on far better terms than he finally came around to, and a hand-picked personal staff put together through five years of screening, whose collective criminal record will blow the minds of high-school American History students for the next 100 years. “

• Rolling Stone #144 (September 27, 1973)

Clearly, HST despised Nixon.  But in his last years he would have preferred Nixon to Bush II.

“This is going to be a very expensive war, and Victory is not guaranteed— for anyone, and certainly not for anyone as baffled as George W. Bush. All he knows is that his father started the war a long time ago, and that he, the goofy child-President, has been chosen by Fate and the global Oil industry to finish it Now. “

• “When War Drums Roll” (September 17, 2001)

That was the political side of HST.  What I most appreciate are the outrageous  and surrealistic descriptions, seemingly jotted down while in a lysergic mania.  From Fear and Loathing in Las Vegas (1971)-

 “The sporting editors had also given me $300 in cash, most of which was already spent on extremely dangerous drugs. The trunk of the car looked like a mobile police narcotics lab. We had two bags of grass, seventy-five pellets of mescaline, five sheets of high-powered blotter acid, a salt shaker half full of cocaine, and a whole galaxy of multi-colored uppers, downers, screamers, laughers and also a quart of tequila, a quart of rum, a case of Budweiser, a pint of raw ether and two dozen amyls. All this had been rounded up the night before, in a frenzy of high-speed driving all over Los Angeles County — from Topanga to Watts, we picked up everything we could get our hands on. Not that we needed all that for the trip, but once you get locked into a serious drug-collection, the tendency is to push it as far as you can.
The only thing that really worried me was the ether. There is nothing in the world more helpless and irresponsible and depraved than a man in the depths of an ether binge. And I knew we’d get into that rotten stuff pretty soon.”

It is hard to tell if HST’s perceptions were shaped by the psychedelic experience or sharpened by it.  I suspect the latter. 

I indulged my need for Polka music yesterday by buying a CD of Oktoberfest music.  Good tunes and no cleaning up after a bunch of drunken Germans.  It was a good day.

Due to a festering project at work I had to miss the Gordon Conference in Newport, RI, this year. I attended the organometallic session last year for the first time and found it to be a very stimulating experience.  Some background for context- My graduate & post-doc training is in organic synthesis. I did my graduate work in a group well known for asymmetric C-C bond forming chemistry in the 80’s. My post-doc was in catalytic asymmetric C-C synthesis with rhodium carbenoids.  It is with this background that I have noticed a bit of a sea change in the big ocean of Organic Chemistry.

At ACS meetings lately it seems that most of the excitement is at the INORG sessions. I’ll qualify that. The excitement for me seems to be at the organometallic sessions. Some pretty stunning work continues to pour out of the labs of the usual rock stars of academia- Bergman, Fu, Grubbs, etc. If you go to INORG talks you could see Harry B. Gray give a rousing account of electron quantum tunneling in enzymes before a packed house. It really is quite a thing to see.

Organic talks at the national meetings seem to be fewer in number than in years past. I don’t have hard numbers, but qualitatively it seems so. Since my grad school time in the 80’s we’ve seen asymmetric synthesis bloom and then go to seed as mechanisms were elucidated and high % ee’s became fairly commonplace. We’ve seen an almost fractal-like growth in catalysts come along to make transformations more efficient. We’ve seen combichem and cheminformatics multiply the efficiency of discovery.

A cryptozoology of hyphenated analytical devices have come along. They can be quite invaluable, but they can choke the budgets of anayltical departments in academia and industry alike, filling disc drives with galaxies of data and graphic user interfaces with an explosion of windows and settings. 

Have I become a Luddite?  No, but I am fussier about commiting hours and hours to learning new software and having to adapt to the machine’s “requirements”.

Obviously, the past 20 years of organic chemistry have been very fruitful. But, the Organometallic people are coming up with the really interesting new examples of organic transformations. Why the lull, why the lack of buzz at ACS meetings in the ORGN sessions? Will the upcoming San Francisco meeting be alight with some new excitement, or will it be a pageant of variations on a theme? I’ll be there to have a look.