ORGLIST: Questionable (?) mechanisms.

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From: Richard Feinman (rumford$##$onebox.com)
Date: Thu Feb 14 2002 - 22:51:20 EST

I don't know about questionable but mechanistic problems that I am interested
in which I'm having a little trouble getting a grip on (although it may
be elementary) are:

1. It's usually assumed that although thioesters are thermodynamically
unstable relative to oxygen esters, the rates of hydrolysis are similar.
 I wonder about the evidence for this. Fedor & Bruice studied trifluoroacetate
esters and I wonder if this is representative.
2. Along the same lines, it is also generally stated that thioesters
are like ketones (due to poor electronegativity of S and limited delocalization).
 Is there comparative data on rates of hydrate formation of ketones relative
to formation of tetrhedral intermediates in ester and thioester hydrolysis
? 

--
Richard Feinman
rumford$##$onebox.com - email
(718) 404-3901 x6280 - voicemail/fax

---- "G. Robert Shelton" <rshelton$##$chem.ufl.edu> wrote:
> orglist-ers,
>
> Just wanted to throw out a general question to the active people of
> the list, and some of those not so active like myself who are waiting
> for phyiscal organic question to be asked. And from there maybe start
> some threads of conversation that would be of interest to some of us
> that are not solely organic synthesis people. Hopefully this is the
> place for this question. So In your opion, what are the most questionable
> chemical mechanisms?
>
> -Robert
>

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