Where has all the (-)-sparteine gone?
by azmanam on Jun 11 2010 (20394 Views)
*Welcome Pipeline readers! No really, if you have a dusty bottle of sparteine, we'll probably take it 
Our lab uses a lot of (-)-sparteine in enantioselective aldol additions, so we tend to buy large bottles which last us a while. As such, we haven't had to order (-)-sparteine in a while. But our bottle is getting low (read: there are a few hundred microliters left), and it's time to order more.
But it's all gone.
All of it.
No one sells (-)-sparteine anymore. Acros. Fisher. Alfa Aesar. VWI. Strem. TCI. I'm sure I'm missing some, since I don't actually do the ordering. Our ordering guy called Aldrich specifically, and was able to order three 10 mL bottles (probably the last available in the world).
Well, today we get a letter from Sigma-Aldrich telling us... they're canceling our order. They're not selling it anymore either.
What is going on, here? Anyone know why the major (-)-sparteine shortage? Is this all of a sudden or has this been happening gradually? Is this related to the acetonitrile pinch, or is this something different? Anyone got any black market (-)-sparteine they want to, er, not sell to us?
Is there any chance that you could use a surrogate compound ? I have a posting on asymmetric deprotonation of piperidine using a (+)-sparteine surrogate. I don't know how hard it would be to synthesize, but it seems like a good option.
http://www.pharmnbiofuel.com/pharmnbiofuel-blog/blog
Yeah, we can use commercially available Hunig's base or TMEDA or even tetramethylpropylenediamine, but sparteine is the best for reaction rates and selectivities. I doubt we would synthesize the sparteine surrogate, but it's an interesting option.
Did you try some of the dealers for sparteine that are listed in the SciFinder ?
The Pacific Northwest is covered in Scotch Broom, which is apparently a good source for sparteine. This link suggests that the concentration is somewhere around 0.23% right about now. I can assure you that there are many Oregonians and Washingtonians who'd be willing to sell you some of that infernal weed.
Er, this one: http://www.herbdatanz.com/scotch_broom_picture_monograph.htm
We joked about growing the plant outside our windows like some people grow their own basil... but I don't think we want to get into the isolation business.
I'm more intrigued as to why there's a shortage.
Oh, absolutely -- it's so weird that it's a huge, complex world, but I'm guessing that The One Guy who makes sparteine went on vacation or got hit by a car or something.
P.S. You'd just need one tiny yellow pod and then you'd have yourself a field, really. Let me know and I can have my sister get you some.
We've got enough kudzu down here... it'd be nice to see something else growing rampantly for a change
Can someone also tell me where in the world all the uranium oxide went?
The starting material for thr synthesis of spartein is not available. TCI officer says.
you may ask who was Sigma/alpha or whoever, where did they buy their sparteine from and track down who actually was making it. you may be able to special order it.
It went to dine in hell?
Hey -
I'm a former Crimmins group member who did a TON of aldols while I was there. The system I used was the Thiazolidinethione auxiliary (S,S) instead of (O,O). It removes the need to use sparteine for many, many aldols. (Sparteine's still the best base, but TEA/NMP works nicely in a pinch) or DIEA/NMP.
http://www.unc.edu/depts/mtcgroup/publications.html
I recommend reading #77 on the list, and I apply the NMP bit a lot in my paper #89 on the list. The thiazolidinethione is easier to work with in almost every case, too. (Plus every acylated thiazolidinethione is a bright, bright yellow making chromatography very trivial.) So... I don't know if it helps in your case, but... Feel free to shoot me an email if you want any more info.
Thanks, dslade! The workarounds will help a lot. We also like the (S,S) aux
You're famous Adam...getting linked from the "In The Pipeline blog"! The comments section below has a suggestion on how to clean up sparteine sulfate pentahydrate, if it's available.
http://pipeline.corante.com/archives/2010/06/16/sparteine_and_other_fine_chemical_shortages.php#comments
I have 125g in lab, but can't give it to you due to liability concerns. They'd rather incinerate unused material than give it away. Seriously. You just can't make this stuff up.
Good luck.
I don't think that has been the first time Adam has been linked from In The Pipeline.
Weird. I ordered 10mL from (canadian) aldrich on june 4th and got it the next day.
[...] his labmates have tried to order (-) sparteine from every supplier in the book, and there’s none to be had. So if anyone has a big dusty bottle of it sitting around, you might drop these desperate chemists [...]
In our database we have the canonical substructure in 35 different forms. Structure query!
The exact isomer indeed does not appear to be available, however. Structure query!
Can we help you to source it?
Would love to know what you are doing with the sparteine and aldol.
Dave Collum
dbc6@cornell.edu
u know whats beautiful? i thought we were out of sparteine in our lab so i dug around and found a 100 mL ampule half full of (-)-sparteine. it was orange, but a beautiful clear liquid after i kugelrohred it over CaH2. and i am about to take that sparteine and use 25 g of it for a large scale asymmetric deprotonation.
I used to sell this in my own company (Advanced Asymmetrics, Inc.) a couple of years ago but my supplier closed down the line for reasons that were not explained to me (and seems to have closed the whole company since then). I suppose everyone used this supplier as Alfa, Acros, Sigma, etc. just started falling like dominoes after that.
I've spent the last couple of years working with various plants trying to get some supply restarted without great luck. I have a couple of suppliers, but none that I have gone to the work to qualify as they are all 4 - 6 times more expensive than the old supplier and at that price I suspect the alternative reagents make a lot more sense.
If you really, truly have to have Sparteine, talk to me but to be honest I'm not pushing the issue until someone has a decent price and confirmed quality.
hi everyone, I would like to know if anyone have found a good supplier for (-)-sparteine. I would like to make some quiral organolitiums and I really need it. I will thank any help. Miguel Angel