Spirocyclopropanation Reaction of para-Quinone Methides with Sulfonium Salts: The Synthesis of Spirocyclopropanyl para-Dienones.

@article{Zhang2016SpirocyclopropanationRO,
  title={Spirocyclopropanation Reaction of para-Quinone Methides with Sulfonium Salts: The Synthesis of Spirocyclopropanyl para-Dienones.},
  author={Xiang‐Zhi Zhang and Ji-Yuan Du and Yuhua Deng and Wen-Dao Chu and Xu Yan and Ke‐Yin Yu and Chun‐An Fan},
  journal={The Journal of organic chemistry},
  year={2016},
  volume={81 6},
  pages={
          2598-606
        }
}
A novel DBU-mediated stereoselective spirocyclopropanation of para-quinone methides with sulfonium salts has been developed on the basis of the mode involving a 1,6-conjugate addition/intramolecular dearomatizing cyclization cascade. This reaction provides a mild and effective method for the assembly of synthetically and structurally interesting spirocyclopropanyl para-dienones. The feasibility for the enantioselective access to such functionalized para-dienones has also been explored by using… 
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100 Citations

Tandem Spirocyclopropanation/Rearrangement Reaction of Vinyl p-Quinone Methides with Sulfonium Salts: Synthesis of Spirocyclopentenyl p-Dienones.

The unprecedented reactivity of p-VQMs was explored for the first time in the spiroannulation cascade, providing a stereoselective approach to the construction of synthetically interesting, densely functionalized spirocyclopentenyl p-dienones.

Diastereoselective synthesis of spiro-cyclopropanyl-cyclohexadienones via direct sulfide-catalyzed [2 + 1] annulation of para-quinone methides with bromides.

An efficient sulfide-catalyzed [2 + 1] annulation of para-quinone methides (p-QMs) with diverse bromides has been achieved, displaying good functional group tolerance as well as gram-scale capacity.

P(NMe2)3-Mediated Umpolung Spirocyclopropanation Reaction of p-Quinone Methides: Diastereoselective Synthesis of Spirocyclopropane-Cyclohexadienones.

Significantly, cyclic and acyclic topological structures of α-keto carbonyls as 1,1-dipole one-carbon synthons have a distinct influence on the stereochemistry of products, showing a reversal of diastereoselectivity in this P(NMe2)3-mediated umpolung spirocyclopropanation.

Enantioselective Spirocyclopropanation of para-Quinone Methides Using Ammonium Ylides

The use of Cinchona alkaloid-based chiral ammonium ylides allows for the first highly enantioselective and broadly applicable spirocyclopropanation reactions of para-quinone methides. This strategy…

Synthesis of Diaryl Diazaphosphonates via 1,6-Hydrophosphonylation of p-Quinone Methides with N-Heterocyclic Phosphine-Thioureas.

A mild, efficient method for the synthesis of diaryl diazaphosphonates via 1,6-hydrophosphonylation/aromatization of p-quinone methides (p-QMs) with N-heterocyclic phosphine-thioureas has been…

1,6-Conjugate sulfonylation of para-quinone methides: An expedient approach to unsymmetrical gem-diarylmethyl sulfones

A thermal decarboxylative Cloke–Wilson rearrangement of dispirocyclopropanes derived from para-quinone methides and bromo-Meldrum's acids: an approach to synthesize spirobutyrolactone para-dienones

An unprecedented approach to synthesize spirobutyrolactone para-dienones from para-quinone methides and bromo-Meldrum's acids has been developed and their unique reactivities have been explored for the first time in the thermal decarboxylative Cloke–Wilson rearrangement reaction.

Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

The synthetic utility of the TosMIC protocol was demonstrated in the synthesis of difluoroalkylated diarylmethane 5 and diaryl methane ketone derivatives 6 and 7, which are important core structures in natural products and medicines.

One-pot synthesis of indoles and quinolinones from ortho-tosylaminophenyl-substituted para-quinone methides

A facile one-pot synthesis has been developed through alkylation/acylation of ortho-tosylaminophenyl-substituted para-quinone methides followed by an intramolecular 1,6-conjugate addition and oxidation sequence, providing a divergent synthetic approach to structurally diverse 2,3-disubstituting indoles and 3,4-diaryl-subStituted quinolinones.

Enantioselective Synthesis of Functionalized 4-Aryl Hydrocoumarins and 4-Aryl Hydroquinolin-2-ones via Intramolecular Vinylogous Rauhut-Currier Reaction of para-Quinone Methides.

This intramolecular mode for the catalytic enantioselective 1,6-conjugate addition of p-QMs has been explored for the first time, delivering two types of synthetically important heterocycles in high yields and enantiOSElectivites.
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