[movies]

for aryl ethers, simple koh followed by methyl iodide (or eq)...or dimtheyl sulfate (or equiv) could be used.

for alkyl ethers, use williamson ether synth.

This would be to make the ether, not cleave it, yes?

[movies]

Okay, tough one:

Benzyl alcohol to methyl benzoate in one step.

[GCT]

Br-benzene +Mg+ Br-allyl
BH3/HOOH/OH
Swern O

woa back up a minute here, why don't you show us a diagram (using chemical software).  I'm guessing that you would want the grinard complex to attack the terminal halogenated carbon right?  It would probably work, being a terminal allyl carbon.  However, have we considered whether the double bond would be a problem?

could Br-benzene+Mg+Br-allyl be completed within one experimental step?

[GCT]

Okay, tough one:

Benzyl alcohol to methyl benzoate in one step.

I've seen this in Designing Organic Synthesis, unfortunately I don't have the book with me.  It's quite simple really, from what I remember, some sort of modified oxidation, with a little twist from the standard.

[KC]

To GCT  

1. sorry, havent downloaded chemdraw on this computer
2. gringards readily participate in SN2 reactions such as the one I mentioned...gringard is the nucleophile, allyl bromide is the electrophile. this rxn would have to be done in THF, as SN2 substitutions are best carried out in polar aprotic solvents.
2. gringards do not react with double bonds.. that's just a fact of organic chemistry ...double bonds can react with a number of lewis acids, but not lewis bases!!!
3. now, why dont you propose a new question for us

[KC]

GCT--
this may work in -'one pot'...
KmnO4/ OH will give the carboxylate salt...,
adding diazo methane in situ would give methyl benzoate (as diazo methane and carboxylates are known to give esters, and release N2.
I am sure that there are more elegant ways to affect this transformation

[movies]

2. gringards do not react with double bonds.. that's just a fact of organic chemistry ...double bonds can react with a number of lewis acids, but not lewis bases!!!

Well, this is sort of a special case because there is the possibility of an S_N2' attack on allyl bromide as well.  That would involve the Grignard reagent reacting with the allyl group.  Hard to tell the difference between the two mechanisms though because the product is the same.  You might be able to differentiate the two attacks with a deutero labelled allyl bromide.

Also, the magnesium ion is a pretty good Lewis acid, so don't discount Grignard reagents as solely Lewis bases.

[GCT]

GCT--
this may work in -'one pot'...
KmnO4/ OH will give the carboxylate salt...,
adding diazo methane in situ would give methyl benzoate (as diazo methane and carboxylates are known to give esters, and release N2.
I am sure that there are more elegant ways to affect this transformation

hmm....pretty neat, I'll have to look into this a bit more.  Movies, is this what you had in mind?  Let's resolve this brainteaser before moving on.

[KC]

come on, movies...do tell...
benzyl alcohol to methyl benzoate

[GCT]

come on, movies...do tell...
benzyl alcohol to methyl benzoate

He's actually gone for the moment, will be back monday or perhaps tuesday at the latest.  Guess we'll need to wait till then

[movies]

Sorry, was out of town for the weekend.  The reaction I was thinking of is a modified procedure for benzyllic oxidation with MnO₂.  If you run the reaction in methanol solvent with added sodium cyanide, then the methyl ester is formed in one reaction process.  A neat trick, I think.

Corey first reported this (J. Am. Chem. Soc. 1968, 90, 5616-5617).

[KC]

Very neat, indeed.  We should expect nothing less from Corey: (He's still going strong at Harvard as we speak.)
Can we work through the mechanism::
1. benzyl alcohol to benzaldehyde
2. addition of cyanide to the carbonyl (aldol rxn)
3. anionic oxygen the previously was carbonyl oxygen takes a proton from methanol
4. methoxide attacks the cyano group of the aldol adduct
5. the now negatively charges N of the previous cyano group takes the proton from the OH at the benzyl position...

6. Any suggestions for the rest of the mechanism/ and or corrections for the fisrt part??

[movies]

Well, first of the cyanide addition isn't an aldol process, it's a Strecker type addition, but regardless it's okay up to that point.  The key is the once the cyanide adds into the aldehyde you have what amounts to a benzyl alcohol derivative, which is again oxidized by MnO₂.  The product is an acyl cyanide, which is quite reactive (see Mander's Reagent).  It turns out that CN- is a better leaving group than MeO-, so methanol exchanges in a process similar to trans-esterification.

The mechanism for oxidation by MnO₂ in itself is pretty interesting.  Anyone care to take a stab at it?

Mander's reagent reference: Tetrahedron Lett. 1983, 24, 5425-5428.

[KC]

I like IT!!
sorry about the aldol reference.
i didnt take into acct that MnO2 would be coming into play a second time.

[movies]

I like IT!!
sorry about the aldol reference.
i didnt take into acct that MnO2 would be coming into play a second time.

Heh.  It's a tricky one indeed.  MnO₂ is such a poor oxidant that you usually have to use around 5 equivalents of it, even for a regular alcohol oxidation (to a ketone or aldehyde).