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. 
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.
Regioselective Carbonylation of 2,2-Disubstituted Epoxides: An Alternative Route to Ketone-Based Aldol Products.
TLDR
Mechanistic studies revealed epoxide ring-opening as the turnover limiting step, an insight that facilitated the development of improved reaction conditions using weakly donating, ethereal solvents.
Synthesis of Enantioenriched Bromohydrins via Divergent Reactions of Racemic Intermediates from Anchimeric Oxygen Borrowing.
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.
Total Synthesis of Tetrahydrolipstatin and Stereoisomers via a Highly Regio- and Diastereoselective Carbonylation of Epoxyhomoallylic Alcohols
TLDR
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.
Nucleophilic ring opening of trans-2,3-disubstituted epoxides to β-amino alcohols with catalyst-controlled regioselectivity.
TLDR
The regioselectivity in the cationic aluminum salen catalyst system is catalyst controlled and allows selective nucleophilic ring opening of unbiased trans-epoxides.
Efficient Synthesis of γ‐Lactones by Cobalt‐Catalyzed Carbonylative Ring Expansion of Oxetanes under Syngas Atmosphere
A practical route from oxetane or thietane to γ‐(thio)butyrolactone via solvated‐proton‐assisted cobalt‐catalyzed carbonylative ring expansion under syngas atmosphere has been established. A wide
Ring‐Expanding Carbonylation of Epoxides
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
An Approach to Peri-Fused Heterocycles: A Metal-Mediated Cascade Carbonylative Cyclization/Dearomatic Diels-Alder Reaction.
TLDR
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.
Nucleophilic Transformations of Lewis Acid-Activated Disubstituted Epoxides with Catalyst-Controlled Regioselectivity.
TLDR
This Perspective highlights various regioselective transformations of disubstituted epoxides, emphasizing those that have inspired the production of challenging, catalyst-controlled processes.
...
...

References

SHOWING 1-10 OF 67 REFERENCES
Regioselective carbonylation of trans-disubstituted epoxides to β-lactones: a viable entry into syn-aldol-type products.
Two new catalysts are reported for the regioselective carbonylation of trans-disubstituted epoxides to cis-β-lactones. The two catalysts display high and opposing selectivities, which generally are
Phosphine-catalyzed asymmetric synthesis of beta-lactones from arylketoketenes and aromatic aldehydes.
In this paper, the development of a chiral phosphine-catalyzed formal [2 + 2] cycloaddition of aldehydes and ketoketenes that provides access to a variety of highly substituted beta-lactones (14
Highly diastereoselective anti-aldol reactions utilizing the titanium enolate of cis-2-arylsulfonamido-1- acenaphthenyl propionate.
[reaction: see text] anti-Aldol reaction of Ti-enolate derived from cis-2-arylsulfonamido-1-acenaphthenyl propionate with representative aldehydes proceeded in excellent yield with high
SN2 Ring Opening of β-Lactones: An Alternative to Catalytic Asymmetric Conjugate Additions
Merging catalytic asymmetric acyl halide-aldehyde cyclocondensation (AAC) reactions with ensuing Grignard-mediated ring opening of the derived enantiomerically enriched β-lactones is presented as a
Formation of Disubstituted β-Lactones Using Bifunctional Catalysis
Acid chlorides and aromatic aldehydes react in the presence of a stoichiometric amount of a tertiary amine and catalytic amounts of a cinchona alkaloid derivative and a Lewis acid to produce
Practical β-Lactone Synthesis: Epoxide Carbonylation at 1 atm
A readily prepared bimetallic catalyst is capable of effecting epoxide carbonylation to produce β-lactones at substantially lower CO pressures than previously reported catalyst systems. A
Titanocene-catalyzed regiodivergent epoxide openings.
TLDR
The first regiodivergent opening of unbiased epoxides providing the ring-opened products in high enantiomeric excess from racemic and exceptionally high enantioenriched substrates in a double asymmetric process has been devised.
Enantioselective and collective syntheses of xanthanolides involving a controllable dyotropic rearrangement of cis-β-lactones.
Let's swap: a scalable, atom-economic, enantio-, and diastereoselective synthetic route to trisubstituted γ-butyrolactones based on a Wagner-Meerwein-type dyotropic rearrangement of cis-β-lactones is
Asymmetric synthesis of bicyclic beta-lactones via the intramolecular, nucleophile-catalyzed aldol lactonization: improved efficiency and expanded scope.
TLDR
The intramolecular, nucleophile-catalyzed, aldol lactonization (NCAL) process merges catalytic, asymmetric carbocycle synthesis with beta-lactone synthesis with greatly improved conversion and efficiency and shorter reaction times with no diminution of enantioselectivity.
Carbonylation of Epoxides
Development in the field of transition metal-catalyzed carbonylation of epoxides is reviewed. The reaction is an efficient method to synthesize a wide range of β-hydroxy carbonyl compounds such as
...
...