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

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 coc...

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Published inOrganic letters Vol. 18; no. 13; pp. 3210 - 3213
Main Authors Sommer, Heiko, Fürstner, Alois
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 01.07.2016
Amer Chemical Soc
Subjects
antibiotics
benzoquinones
chemical reactions
Chemistry
Chemistry, Organic
methanol
moieties
oxidants
Physical Sciences
Science & Technology
PALLADIUM
KETONES
CATALYSIS
ALKOXYCARBONYLATION
CARBAMOYLATION
COMPLEXES
ALDEHYDES
INTERNAL ALKYNES
TRANS-HYDROGENATION
NOCARDIA SP
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Summary: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.
Bibliography:ObjectType-Article-1
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ISSN:1523-7060
1523-7052
1523-7052
DOI:10.1021/acs.orglett.6b01431