My New Favorite Reaction

January 28th, 2007

Move over, Bingel cyclopropanation… I’ve got a new favorite reaction.

While thumbing through a review article on the chemistry of some “extraordinary Maillard flavor compounds,” I came upon this little diddy:

Magnificent! While I don’t want to make a habit of encroaching on Milo’s territory of posting organic reaction mechanisms, you’ll find one after the jump. See if you can figure it out before peeking…

It starts out in a manner similar to thiol-disulfide interchange, but continues with the oxidized phosphorus intermediate serving as an activating agent for the carboxylic acid to react with the thiolate that is released. Thus, the byproducts of the initial redox reaction are an activating agent and a nucleophile. Saucy!

While I’ve never seen it before, a quick search of the literature reveals that the reaction was first reported way back in 1970 by the great Mukaiyama (Bull. Chem. Soc. Japan, 1970, 43, 2632). With apologies to the atom economists among you, this transformation is the bee’s knees. If it worked in water, it might be the greatest reaction ever.

Previous Comments

  1. My Lord, My Guide Says:
    January 29th, 2007 at 12:15 am I am happy to see some chemistry here finally.
  2. Paul Says:
    January 29th, 2007 at 12:22 am Touché.
  3. excimer Says:
    January 29th, 2007 at 12:53 am DIdn’t Tenderbutton have a post on how much triphenylphosphine oxide blows? Because I certainly mirror that sentiment. I used to think the Mitsunobu inversion was an amazing reaction, until I had to do a bunch of them.Yeah, yeah, and everyone has their own little secret for getting rid of PPh3O, but I really like mine: either use the PPh3 bound to polystyrene, or… just don’t do those reactions where it’s a byproduct. Easy as pie, either way.
  4. milkshake Says:
    January 29th, 2007 at 1:18 am I use trimethylphosphine whenever possible. Smells like garlic in rancid gasoline but the oxide extracts into water easily. Also some Aza-Wittigs go much better with Me3P than PPh3
  5. Paul Says:
    January 29th, 2007 at 3:41 am Excimer: Yeah, the organophosphine oxides suck. I think that Ph3PO might be neck-and-neck with dicyclohexylurea (DCU = hydrated DCC) for the most hated common byproducts in organic chemistry.
  6. Mitch Says:
    January 29th, 2007 at 4:11 am Once triphenylphosphine derivatives are in a mass spec column, always triphenylphosphine derivatives are in a mass spec column. Grrrrrr….Mitch
  7. milo Says:
    January 29th, 2007 at 6:55 am Triphenylphosphine oxide and DCU are only a pain if you don’t know how to work with them. Most organic chemists also hate DMF, DMAC and DMSO… until they learn the tricks o’ the trade.I will concede though that DCU is a particular pain in the rear, but we have EDC an other coupling agents.
  8. Ψ*Ψ Says:
    January 29th, 2007 at 10:05 am Knowing how to get rid of DMF doesn’t mean I like it any more.
  9. XXXyzrt Says:
    January 29th, 2007 at 12:29 pm This also the carboxylic acid activation in the Corey-Nicolaou macrolactonization
  10. Uncle Al Says:
    January 29th, 2007 at 2:07 pm Sulfonated Ph3P is water-soluble. Possiblities exist…
  11. joel Says:
    January 30th, 2007 at 3:04 pm Adding a C60 or a carbon nanotube would sexify this reaction considerably.
    Better yet, a inorganic nanowire pimped out with some magnetic impuritiez.
  12. Amadeus Says:
    January 30th, 2007 at 7:42 pm I was studying this Bingel reaction during my undergrad, it gets more interesting when you try to put more than one adduct in the buckyball since you get a bunch of regioisomers, controling the selectivity of the second addition is done by tethering two alpha-halo malonic esters with a semirigid linker than can be cleaved after works. In this way people like Andreas Hirsh is able to modify selectively the two poles of the buckyball. Pretty cool stuff,
    This reaction shares some similarity with the Darzen condensation for the formation epoxides.…..Darzen.htm
  13. Paul Says:
    January 30th, 2007 at 7:49 pm I also worked with fullerenes as an undergrad. And Hirsch’s work is great–a lot of people, including my advisor, refer to the reaction as the Bingel-Hirsch Reaction.
  14. karsten Says:
    March 4th, 2007 at 10:14 am Is the bingel reaction a [2+2]or a [3+2]?
  15. Paul Says:
    March 4th, 2007 at 12:36 pm The Bingel is a [2+1], although it is not a pericyclic reaction, so I use that nomenclature with hesitation.An example of a [2+2] addition to C60 would be the photoaddition of a,b-unsaturated ketones. An example of a [3+2] addition to C60 is the 1,3-dipolarcycloaddition of azomethine ylides (the Prato reaction).
  16. karsten Says:
    March 5th, 2007 at 3:48 am thx a lot for the reply, it helped a lot

One Response to “My New Favorite Reaction”

  1. GamerLup Says:



    , Graffiti

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