Retro-metal-ene versus retro-Aldol: mechanistic insight into Rh-catalysed formal [3+2] cycloaddition.

@article{Liu2018RetrometaleneVR,
  title={Retro-metal-ene versus retro-Aldol: mechanistic insight into Rh-catalysed formal [3+2] cycloaddition.},
  author={Song Liu and Tao Zhang and Lei Zhu and Kangbao Zhong and Jianxian Gong and Zhen Yang and Ruopeng Bai and Yu Lan},
  journal={Chemical communications},
  year={2018},
  volume={54 96},
  pages={
          13551-13554
        }
}
Theoretical calculations have been performed to investigate the mechanism and stereoselectivity of rhodium-catalysed intramolecular [3+2] cycloaddition for construction of a substituted hexahydropentalene complex. A new C-C bond cleavage mechanism, retro-Aldol-type, is proposed and verified for this Rh-catalysed [3+2] cycloaddition reaction. 
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References

SHOWING 1-10 OF 40 REFERENCES

Gold-catalyzed [3+2] cycloaddition/hydrolytic Michael addition/retro-aldol reactions of propargylic esters tethered to cyclohexadienones.

Under strictly dry conditions, cyclohexadienones (I) and (III) rearrange to tricyclic products, whereas under air in the presence of usual moisture bicyclic furans of type (VI) and (VIII) are

Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reactions of 1-ene-, 1-yne- and 1-allene-vinylcyclopropanes.

New Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reactions of 1-ene-, 1-yne and 1-allene-vinylcyclopropanes have been developed, affording an efficient and versatile synthesis of

Effective Chirality Transfer in [3+2] Reaction between Allenyl-Rhodium and Enal: Mechanistic Study Based on DFT Calculations.

TLDR
Theoretical calculation was performed to study the chirality transfer in a newly reported intramolecular cycloaddition of enal and alleno rhodium species, generated in situ from an enynol precursor, predicting that only the cis [3.3.0] bicyclic product could be generated, regardless of either erythro or threo substrate.

Enantioselective total synthesis of (+)-Lingzhiol via tandem semipinacol rearrangement/Friedel-Crafts type cyclization.

TLDR
The (+)-Lingzhiol synthesis is the first example of in tandem semipinacol rearrangement reactions, the migrated aryl group further reacting with the carbonyl oxonium electrophile to furnish a polycyclic skeleton.

Formal Total Synthesis of (±)-Lycojaponicumin C.

TLDR
The formal total synthesis of (±)-lycojaponicumin C has been accomplished using a Rh-catalyzed formal [3 + 2] cycloaddition reaction to construct the bicyclic [3.3.0] scaffold bearing two vicinal quaternary carbon centers.

Asymmetric intramolecular carbocyanation of alkenes by C-C bond activation.

TLDR
Ni (0) and Pd(0) complexes act as catalysts in the intramolecular aryl- and acylcyanation reactions, respectively, of alkenes, which can furnish valuable heterocycles such as oxindoles, which are precursors for a myriad of natural and/or biologically active products.

Organocatalytic Asymmetric Michael/Hemiketalization/Retro-aldol Reaction of α-Nitroketones with Unsaturated Pyrazolones: Synthesis of 3-Acyloxy Pyrazoles.

An organocatalytic asymmetric cascade Michael/hemiketalization/retro-aldol reaction between unsaturated pyrazolones and α-nitroketones is described. A bifunctional thiourea catalyst was found to be

Enantioselective Ruthenium-Catalyzed Benzocyclobutenone-Ketol Cycloaddition: Merging C-C Bond Activation and Transfer Hydrogenative Coupling for Type II Polyketide Construction.

TLDR
Using this method, the "bay region" substructure of the angucycline natural product arenimycin was prepared and the first enantioselective intermolecular metal-catalyzed cycloadditions of benzocyclobutenones via C-C bond oxidative addition are described.

Asymmetric total synthesis of (-)-lingzhiol via a Rh-catalysed [3+2] cycloaddition.

TLDR
An efficient [3+2] cycloaddition reaction between an enal and an alleno rhodium species, which was generated in situ from the corresponding enynol via a retro metal-propargylation reaction, to give bicyclic systems bearing two quaternary atoms at their bridgehead positions is reported.

Modular Access to Azepines by Directed Carbonylative C–C Bond Activation of Aminocyclopropanes

TLDR
A modular Rh-catalyzed entry to azepines is outlined, and byproduct-free heterocyclizations are enabled by sequential C–C activation and C–H functionalization steps.