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Topic: A question on Corey-House synthesis  (Read 10070 times)

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Offline kkiddu

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A question on Corey-House synthesis
« on: July 12, 2010, 06:03:13 PM »
Hi guys. This is my first post here, so please excuse me if I mess something up.

Here're my questions.

What's the role of a carbanion in the last step of Corey House Synthesis ?

Specifically:-

R2CuLi + R'X  :rarrow: R-R'

And why does R' have to be 1o ?

Thanks. A lot.

Offline SVXX

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Re: A question on Corey-House synthesis
« Reply #1 on: July 13, 2010, 04:24:38 AM »
First of all, dialkyl lithium cuprates are also known as Gilman reagents, which you must be knowing(R2CuLi that is). In these types of organometallic reagents, the alkyl part acts as the anion, which you must also be knowing.
Gilman reagents are weakly polarised, i.e., the negative charge which appears on R is not strong enough(unlike in RLi where the negative charge is quite strongly polarised). Thus Gilman reagents cannot act on alkyl halides which are sterically hindered, as the carbanion so formed would not be strong enough to go through the nucleophilic substitution (SN2). Hence the halides must be primary.
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Offline g-bones

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Re: A question on Corey-House synthesis
« Reply #2 on: July 13, 2010, 06:55:57 AM »
First of all, dialkyl lithium cuprates are also known as Gilman reagents, which you must be knowing(R2CuLi that is). In these types of organometallic reagents, the alkyl part acts as the anion, which you must also be knowing.
Gilman reagents are weakly polarised, i.e., the negative charge which appears on R is not strong enough(unlike in RLi where the negative charge is quite strongly polarised). Thus Gilman reagents cannot act on alkyl halides which are sterically hindered, as the carbanion so formed would not be strong enough to go through the nucleophilic substitution (SN2). Hence the halides must be primary.

just a quick note,
In the strictest sense, the Gilman reagent is the dimethyl cuprate.  although it has become commonplace to simply refer to all organocuprates as Gilman reagents.  Just in case you run into someone quite picky about naming  ;) 

Offline SVXX

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Re: A question on Corey-House synthesis
« Reply #3 on: July 13, 2010, 10:56:11 AM »
Aight thanks for the tip :)
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Offline kkiddu

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Re: A question on Corey-House synthesis
« Reply #4 on: July 14, 2010, 01:41:20 PM »
First of all, dialkyl lithium cuprates are also known as Gilman reagents, which you must be knowing(R2CuLi that is). In these types of organometallic reagents, the alkyl part acts as the anion, which you must also be knowing.
Gilman reagents are weakly polarised, i.e., the negative charge which appears on R is not strong enough(unlike in RLi where the negative charge is quite strongly polarised). Thus Gilman reagents cannot act on alkyl halides which are sterically hindered, as the carbanion so formed would not be strong enough to go through the nucleophilic substitution (SN2). Hence the halides must be primary.

Oh...totally forgot about my question. Thanks a lot.

Offline orgopete

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Re: A question on Corey-House synthesis
« Reply #5 on: July 17, 2010, 06:09:55 PM »
I don't know why primary halides are required, but I don't think it is due to steric hindrance. I think it is due to decreased reactivity. I have speculated on a mechanism here:
http://orgo.curvedarrow.com/punbb/viewtopic.php?id=337
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