67428-13-1

Upstream product

• 53723-50-5 2-methylenecyclohexyl acetate 
• 18424-76-5 dimethyl malonate sodium salt 
• 108-59-8 malonic acid dimethyl ester 
• 5330-61-0 1-nitromethyl-cyclohexene 
• 86365-78-8 2-bromo-1,6-heptadiene 
• 927832-71-1 C₁₂H₂₀O₃ 

Relevant academic research and scientific papers

Consecutive carbon-carbon bond formation via the π-allylpalladium variant of the Heck reaction

Two C-C bonds are readily formed by nucleophilic addition of stabilized carbanions to the π-allylpalladium intermediate regioselectively produced by the Heck reaction of a vinyl bromide and an unactivated olefin. An intramolecular version of this condensation gives functionalized carbobicyclic compounds as products.

Reactions of some alken-1-yl and cycloalken-1-yl bromomethyl sulfones with dimethyl malonate and malononitrile

Bromomethyl cyclopent-1-enyl sulfone and bromomethyl cyclohex-1-enyl sulfone reacted with dimethyl malonate and malononitrile sodium salts in THF at 20-50°C to give products of Michael-induced Ramberg-Baecklund reaction, functionalized derivatives of meth

Iron-catalyzed allylic alkylation

A method for performing an iron-catalyzed allylic alkylation includes the preparation of a reaction mixture obtainable from (i) an allylic substrate with the structural element C═C—C—X, wherein X comprises a leaving group that represents a carbonate, (ii) an active Fe(-II) catalyst complex, (iii) at least one ligand, (iv) at least one solvent, and (v) a nucleophile or pronucleophile.

A Palladium-Mediated Tandem Carbon-Carbon Bond Forming Method Featuring Nucleophilic Substitution of Intermediate ?-Allylpalladium Complexes Produced via the Heck Reaction

Carbon nucleophiles are alkylated with ?-allylpalladium complexes formed by the palladium-catalyzed Heck reaction of a vinyl bromide and an olefin.This methodology achieves the consecutive formation of two carbon-carbon bonds in one simple operation and can be applied both inter- and intramolecularly.The rapid construction of functionalized carbobicyclic compounds is effected by the intramolecular version of this condensation.

REGIOCHEMICAL DIVERSITY IN ALLYLIC ALKYLATIONS VIA MOLYBDENUM CATALYSTS

The use of molybdenum as a template to control regioselectivity in allylic alkylations is explored.The feasibility of performing allylic alkylations with preformed ?-allylmolybdenum comlplexes is established.As in palladium reactions, addition of excess phosphine has a profound effect on the rate these reactions.A catalytic reaction based upon molybdenum hexacarbonyl is developed.Using malonate anion, excellent regioselectivity for attack at the more substituted end of an allyl system regardless of the positional identity of the initial leaving group exists.With β-ketoesters, substrates which possess a secondary and a primary carbon in the allyl unit lead to preferential attack at the secondary carbon.However, substrates that possess a tertiary and a primary carbon at the termini lead to attack at the primary carbon.Anions derived from substituted malonates and 1,3-diketones lead to substitution at the less substituted position of allyl systems.The presence of strongly electron withdrawing substituents has little effect on these orientational blases.Mechanistic implications of these results are discussed.

Palladium-Catalyzed Substitutions of Allylic Nitro Compounds. Regiochemistry

Primary, secondary, and tertiary allylic nitro compounds underwent Pd(0)-catalyzed allylic substitution by stabilized carboanions, secondary amines, and benzenesulfinate ion (PhSO2-). α,β-disubstituted α-nitro olefins also behaved as allylic nitro compounds, via base-catalyzed vinyl -> allyl rearrangement, and underwent allylic substitution by secondary amines and PhSO2-.The regiochemistry of these substitutions was dependent on the structure of the allylic nitro compound amd on the steric bulk of the nucleophile.Generally, substitution occurred at the lesshindered or least substituted site.In some cases added or generated NaNO2 affected the regioselectivity of the allylic substitution of allylic nitro compounds and some allylic acetates by PhSO2-.Under these conditions, the more sterically hindered allylic sulfones were formed.