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Posted by
Junaid Urrehman

Grignard Addition to Propylene Oxide

Barry Austern  Follow
rolnor,

You saw no Payne rearrangement?

I have a reference that adds an aliphatic Grignard to propylene oxide utilizing catalytic CuI.  They do report minor Wurtz products which is kind of annoying.  I am going to try it because it is an easy reaction. 

We shall see.

Cheers!

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David Bernheim  Follow
Here is the reaction I made, dont remember the yield:

https://pubs.acs.org/doi/10.1021/jo00009a012

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Nuel Rosson  Follow
Best to make the dialkyl magnesium cuprate and make BF3-complex, then mix with the epoxide. I think its simmilar to dialkyl lithium cuprates. I have reacted grignard with secondary epoxide with good yield so I am not sure if cuprate is neccesary. HMPA would probably speeed things up. In your case the epoxide is not sterically hindered so maybe its very easy.

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Andreas Buehler  Follow
Addition of Grignard reagents to ethylene oxide, is described in various editions of the Vogel’s Textbook of Practical Organic Chemistry (Chapter: Aliphatic alcohols). For example, in the 5th Edition, this corresponds to the pages 535-537. However, the obtained yields are rather moderate (50-70%). 
Anyway and in the case of propylene oxide, you will get a mixture of alcohols and the secondary alcohol will probably be the major product.

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