Latest piece for the RSC in the July issue of Chemistry World…
The final deprotection is actually not so surprising at all. It is well known that in 1,3-phenolic ketones, the OMe can be easily deprotected under relatively mild conditions because the product structure is stabilized by an intramolecular hydrogen bond between the phenolic OH and the ketone (six membered ring). There are plenty of cases where simple heating to 60 C with pTSA will do the trick while the other phenolic OMe’s require BBr3 for deprotection.
I selectively take off OMe’s like this all the time. BCl3 and AlCl3 work well, leaving all phenolic OMe’s not H-bonded alone.
i need help:i’m trying to do a methilenation(metilentriphenilphosphoniumbromide,sodium hydride,DMSO)on a beta keto ester..any references?Thanks a lot.
Madforit: is that the Eschenmoser Reaction??
i work a bit with that kind of chemistry. i have many references that can help.
BTW, great job Paul. keep going..
no it’s “just”a simple wittig reaction…but i m going mad…probably the phosphorous ilide act as a base for tha active methilene H’s,i don t know,i have a mixuture after column …
Thanks a lot.
…not a mixture after column,but something that i can t explain
you will always have a problem as long as you have ester beta to carbonyl – because of the facile enolisation, and also the product, beta C=C ester will like to equilibrate to conjugated one.
You can try dimethyl titanocene, it should be less basic than Witting and there is a good Orgsyn procedure for it, from Cp2TiCl2 and Me-Grignard. Also check the Petatis original paper, I think it was in a JACS from early 90s and if I remember it works on enones and tetralones – and those are easily enolisable substrates.
thanks a lot,the alternative strategies was petasis titanocene or protection of carbonyl mojety..
So, in terms of these wittig reactions, suppose you don’t want to just methyleneate the carbonyl and instead you’d like to use, say, the propyl Wittig derivative. Is there any hope of ever doing such a reaction?
Also, Madforit, not sure if this helps, but sometimes it’s worth remembering it’s possible to do a wittig in two ways. You could also reduce your ketone, turn into bromine, make wittig salt and attack the aldehyde of whatever you had. It’s def. more steps, but it’s an alternative. I suppose you’d still have to worry about the enolization issue with the ylide, but…..
any procedure for the selective protection of the ester mojety beta to a ketone?