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Hydroxyl-Assisted Carbonylation of Alkenyltin Derivatives: Development and Application to a Formal Synthesis of Tubelactomicin A

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journal contribution
posted on 09.06.2016, 16:24 by Heiko Sommer, Alois Fürstner
Alkenyltin derivatives flanked by a hydroxyl group are subject to methoxycarbonylation when treated with catalytic amounts of Pd­(OAc)2 and Ph3As in MeOH under a CO atmosphere; key to success is the use of 1,4-benzoquinone as a stoichiometric oxidant in combination with trifluoroacetic acid as a cocatalyst. The acid lowers the LUMO of the quinone and likely marshals the critical assembly of the substrates. Under the optimized conditions, competing proto-destannation is marginal; the method proved compatible with various (acid sensitive) functional groups and was applied to a short formal total synthesis of the antibiotic tubelactomicin A.