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Topic: Anti-Markovnikov hydrosilylation of an alkene  (Read 3577 times)

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Offline opsomath

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Anti-Markovnikov hydrosilylation of an alkene
« on: February 04, 2014, 08:33:59 PM »
Hi all, I have a summer project involving synthesizing some terminal silanes. Generally, the plan is to create silanes by reacting R3-SiH species with alkenes through catalytic hydrosilylation. Are any of you familiar with this reaction? What catalysts or coreagents do you use for it?

Offline TheUnassuming

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Re: Anti-Markovnikov hydrosilylation of an alkene
« Reply #1 on: February 05, 2014, 11:31:54 AM »
Aside from the alkene, what other functionalities are present? 
The combinations seem to vary a little, but a Pd source like Pd(PPh3)4 and a base like morpholine seems common enough.  Other catalyst options used commonly are RhCl(PPh3)3 and H2PtCl6. 
Do you have much journal access?
When in doubt, avoid the Stille coupling.

Offline opsomath

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Re: Anti-Markovnikov hydrosilylation of an alkene
« Reply #2 on: February 05, 2014, 04:44:57 PM »
I have used only chloroplatinic acid in the past. I have journal access but it requires a physical trip to my campus library - if you have a reference you like, shoot it to me and I'll get it when I'm over there.

Typical molecules I will use will have an aryl ketone, an aryl halide, possibly a ferrocene...no protic or particularly reactive species.

Ever tried Pd/C or Pt/C?

Offline TheUnassuming

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Re: Anti-Markovnikov hydrosilylation of an alkene
« Reply #3 on: February 06, 2014, 09:50:08 AM »
I've never used those two in particular and don't readily see any references to them being used for that purpose. 
If your substrate isn't too expensive and that is what you have on hand it wouldn't hurt to see if it can work though.
When in doubt, avoid the Stille coupling.

Offline TheUnassuming

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Re: Anti-Markovnikov hydrosilylation of an alkene
« Reply #4 on: February 06, 2014, 09:54:48 AM »
Just talked to a friend on mine who did these reactions on large scale for a chemical supplier.  For almost all the reactions they ran they used Karstedt's catalyst, which looks like its still in heavy rotation in current literature.
When in doubt, avoid the Stille coupling.

Offline opsomath

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Re: Anti-Markovnikov hydrosilylation of an alkene
« Reply #5 on: March 03, 2014, 10:10:24 AM »
Thanks for checking on this for me. I was hoping for some magically cheap alternative as I am on a shoestring budget, but it is not to be. :)

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