Enantioenriched β-lactone and aldol-type products from regiodivergent carbonylation of racemic cis-epoxides

@article{Mulzer2014EnantioenrichedA,
  title={Enantioenriched $\beta$-lactone and aldol-type products from regiodivergent carbonylation of racemic cis-epoxides},
  author={Michael Mulzer and W. Chadwick Ellis and Emil B. Lobkovsky and Geoffrey W. Coates},
  journal={Chemical Science},
  year={2014},
  volume={5},
  pages={1928-1933}
}
A new carbonylation catalyst is reported that provides enantioenriched β-lactones and aldol-type products from the carbonylative ring-expansion of racemic cis-epoxides. Detailed analysis of the reaction demonstrates that the epoxide substrates undergo regiodivergent carbonylation reactions instead of traditional kinetic resolutions. This new catalytic system was applied to the synthesis of a key fragment of the antibiotic Globomycin. 
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Carbonylation of cis-disubstituted epoxides to trans-β-lactones: catalysts displaying steric and contrasteric regioselectivity.
TLDR
Two catalysts are presented for the regioselective carbonylation of cis-disubstituted epoxides oftrans-β-Lactones so that either one of the two possible β-lactone regioisomers can be obtained selectively.
Enantioenriched β‐Lactone and Aldol‐Type Products from Regiodivergent Carbonylation of Racemic cis‐Epoxides.
The new catalytic system is also applied to the synthesis of compound (VIII) which is a key fragment of the antibiotic globomycin.
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TLDR
It is reported a chiral phosphoric acid catalyzed bromocyclization/regiodivergent reaction of racemic intermediates sequence, which is enabled by anchimeric oxygen borrowing, and both enantiomers of the bromohydrin products were obtained in generally excellent yields and enantioselectivities.
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A concise enantioselective synthesis of tetrahydrolipstatin and seven stereoisomers has been achieved and demonstrated the practicality of the carbonylation catalyst for complex molecule synthesis as well as its functional group compatibility.
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The regioselectivity in the cationic aluminum salen catalyst system is catalyst controlled and allows selective nucleophilic ring opening of unbiased trans-epoxides.
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This review summarizes the field of metal-catalyzed ring-expanding carbonylation of epoxides. Specifically, epoxide carbonylation to -, -, and -lactones is reviewed, in addition to epoxide…
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The further dearomatic Diels-Alder reaction of the in situ-generated azaphosphacyclohexone with alkenes provides an array of annulated heterodecalins with high molecular complexity and atomic utilization.
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