Grad School Post #1

This begins a new series I’m starting (which will actually last a while, unlike the summer’s “forgotten reactions” series) in which I discuss the research of people I’m interested in at the grad schools I’m applying to. It’s both to help myself in writing statements of purpose and to enlighten you, my readers, on what the future may hold for me. So…it’s pretty much all about me. 🙂

Anyway, the first installment of this series belongs to Dr. M. Christina White and her graduate student Ken Fraunhoffer at the University of Illinois, Urbana-Champaign. They have designed a diastereoselective synthesis of 1,2-aminoalcohols using a palladium(II)/sulfoxide catalyst that bypasses the oxygenation steps that have previously been necessary for allylic amination reactions. The first step is nucleophilic attack by a relatively weakly nucleophilic tosyl carbamate (the nucleophile must be weak enough to not attack the double bond directly). In the example the paper gives, this forms a five-membered ring with an exo vinyl group (thanks Balwin’s Rules! :-D). The vinyl group is transformed to COOH using some nasty RuCl3/NaIO4 condititons, and finally the ring breaks apart by reaction with sodium naphthalene, DME, and 6-M HCl, giving at last the desired 1,2-aminoalcohol.

Only an intramolecular version of the reaction has been studied so far, although White’s group is exploring the possibility of an intermolecular allylic amination. The worst stumbling block is the potential attack of a nucleophile directly on the double bond, instead of on the allylic carbon. Attaining the appropriate nucleophilicity for the aminating agent is key.

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3 Comments

  1. Hey–you might want to ask Excimer, since he’s at UIUC. (Middle-of-nowhere town in cold Illinois is pretty much not acceptable to me–I am definitely, definitely not applying there!) Alternatively–I’m not sure if you ever met him–Jared (undergrad who used to work in my lab) is in her group. If you send questions to me, I’ll try to finagle answers from him.

    Reply

  2. This approach is like steering a car by looking at in the rear view mirror. You’re seeing what’s been done in the past, and not what you are getting into at the present. (Or not. Maybe I’m reading too much into how much this IS your selection process.) You really want to be looking at the entire body of work and make a decision based on that. You want to be the one with the cool publication of something new that some future undergraduate blogger will be drooling over and say “I want that guy/gal as my advisor”, not the guy with publications on how you took a previous cool idea and expanded on it in 18 different ways.

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  3. I see what you mean, but how can I predict what group would lead me to such a cool discovery? The odds are with the groups that have discovered new things in the past, wouldn’t you say?

    In any case, these posts won’t have much to do with my final decision. It’s just kind of a fun thing, and a good excuse to review some literature.

    Reply

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