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Author Topic: one question on the nicolaou's synthesis of abyssomicin  (Read 3095 times)

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lincoln

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one question on the nicolaou's synthesis of abyssomicin
« on: October 31, 2006, 11:24:01 PM »

angew. chem. int. ed. 2006, 45, 3256
"further processing of the phenylthiomethyl r-lactone 9 with the radical anion species derived from catalytic amounts of 4,4'-di-tert-butylbiphenyl and Li metal resulted in the opening of the lactone ring with concomitant olefin formation"
how does this reaction go along? any input is appreciated.
« Last Edit: November 01, 2006, 12:01:31 AM by lincoln »
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Re: one question on the nicolaou's synthesis of abyssomicin
« Reply #1 on: November 01, 2006, 05:53:48 AM »

This is similar to a Birch reduction, but without ammonia.  In this case, the first thing that happens is the Li delivers an e- to the biphenyl system.  This allows for the electron to be "solvated" in organic solution similar to how it is solvated in ammonia.  From the biphenyl radical, the electron is transfered to the phenyl group of the phenyl thioether.  This can then fragment to liberate a thiophenol radical and a carbanion.  The carbanion can then eliminate out the carboxylate adjacent to it, forming the olefin.  The thiophenol radical can then be reduced by a second equivalent of the lithium and you're done.

Does that make sense?
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lincoln

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Re: one question on the nicolaou's synthesis of abyssomicin
« Reply #2 on: November 02, 2006, 12:49:11 AM »

Thanks. That's reasonable.
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