that looks familiar

Check out my new and old motorcycle keys.




I went to go see The Business play on Thursday, and while I was at the show my motorcycle was stolen. Again.

Miraculously, it was also found and returned the next day, with the helmet still attached.



Apparently pushing a motorcycle out of a parking spot and a couple of blocks down the street in front of busy restaurants and bars, all the while bits and peices of the dangling helmet breaking off as you go doesn't alarm anyone.

Oddly the next day someone saw it and thought it shouldn't be there and called the cops, go figure.

After it had been towed to a lot by order of the police ($240, cash only, for almost 2 miles tow), I went and picked it up. The thieves hadn't had much time with it so all they had really done, aside from dropping it a few times, was break open the ignition lock. Luckily I was able to easily hotwire it, after having had some practice in the recent past.

I guess I need to invest in an alarm.

graphical abstract flub

This isn't a terribly big mistake, but still, I wonder why people don't spend more time correcting their papers.

JACS ASAP multicomponent craziness

In this case it's actually in the graphical abstract, and the part that they used color to try to make it more easily understood makes it worse. The blue ethyl group on the diethylzinc becomes the blue methylene in the molecule. First, the ethyl to methylene is a bit of an exotic leap, and even a student should realize, after a moments thought, that's not a trivial transformation. Second, anyone who is familiar with Simmons-Smith chemistry would recognize that diethylzinc plus diiodomethane means zinc carbene, and the ethyl part is not used at all. All they had to do was make the CH₂ of the diiodomethane blue to be correct, and it somehow slipped past them. Too bad.

In unrelated news Alexakis and his crazy phosphoramadites have a nifty new-to-me reaction.

Org Let ASAP

1,4-Addition to aldehydes, and enantioselective no less. Is it general? For a highly specialized reaction, some might say yes, but in truth, no it's not. Is it amazing and life changing? If you aren't Alexakis or one of his researchers working on it then no, no it's not.

However it's still pretty neat, and I expect anyone who had done copper promoted 1,4-additions, and/or enantioselective additions will think it's pretty neat.

nice legs

I took the red eye back from ACS last night/this morning and perhaps the best part of the whole deal was this little gem I witnessed while bleary eyed and taxiing towards my gate:



Seems like this wonderful product might also have accessory benefits like toughening up a too-tender box with up to 275 lbs. of resistance!

nice drawing

Today as I was perusing the ASAPs, I came upon this one almost immediately:


The graphic looks like there's a lot going on, I like RCM, and they even have an exclamation point in the title! I had to read on!

Anyway, I was immediately greeted with this Scheme:

And the first line threw me a little. It took me a second to figure out what was wrong with it, and all I can say is that it's most likely a hang over from organic chemistry classes. When [3,3]-rearrangements are covered the professors always hammer home the point to look for potential [3,3]-situations whenever there are double bonds present, count to six from the bonds, etc, etc, and then test heavily over the material. In reality, except for groups that use rearrangement chemistry often, [3,3]-rearrangements are no more common than any other reaction, but the automatic counting and checking remain, like a Pavlovian response. I knew something was wrong with the first reaction, but I couldn't put my finger on it.

I actually had to get out pencil and paper and try to do the reaction as drawn, and I couldn't. First I was irked because it's a pet peeve of mine when people flip or rotate molecules to no real gain, like it appears they have done here with the R groups traveling from the left to the right, but that wasn't the biggest problem. I like to think I know some chemistry, but I couldn't get from starting material to product. I read some of the body text finding "The 1,4-diene-ester 9a was prepared by orthoester Claisen rearrangement of the corresponding 1,5-hexadien-3-ol (8a, Aldrich) with catalytic propionic acid or phenol in the case of 8b7 to afford 9b in refluxing triethyl orthoacetate.", while that reinforced the [3,3] business, it provided no more insight as to why this was so hard to figure out, and it conspicuously only mentions one of the two starting materials. I could easily draw a different reaction that provided the product when R = H, but it wouldn't work when R = Me.

I finally went to the supplemental information, and found the starting materials' names: 1,5-hexadien-3-ol, as expected, and 6-methylhepta-1,5-dien-4-ol which I've drawn for you here:


Eagle eyed observers might notice a small difference in the locations of the alcohol groups with respect to the left hand side of the molecules, as drawn, trying to replicate the way 8a,b are drawn in Scheme 2. It's pretty bad that the editors don't catch shit like this, but how do you fuck this stuff up on your own molecules? I understand that they were doing the same reaction multiple times, and most likely wanted to draw both molecules in one to save space, but it seems like it should have been drawn out the long way at least once during all this. Then the later flipping nonsense would be fairly obvious.

happy pi day

The most useful thing Nicolaou has ever done

I typically think that Nicolaou has contributed very little to the endeavor of total synthesis (unless you count using the same series of 3 reactions over and over again to make 1 mg of huge molecules important). But he has finally done something useful (while still managing to just combine two separate and well established reactions). I could have used this when I was banging my head against a wall for 6 months-a year trying to do an oxidative cleavage.

memory