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Upstream product

• 507-19-7 t-butyl bromide 
• 107847-69-8 1,1-diphenylallyllithium 
• 15424-05-2 6-bromo-5,5-dimethyl-1-hexene 
• 4801-14-3 3,3-diphenylprop-2-en-1-ol 
• 17792-17-5 ethyl 3,3-diphenylacrylate 
• 29555-29-1 3,3-diphenyl-2-propenyl acetate 
• 13389-36-1 6-iodohept-1-ene 
• 3542-14-1 3,3-diphenylpropene 

Relevant academic research and scientific papers

Palladium-Catalyzed Allyl-Allyl Reductive Coupling of Allylamines or Allylic Alcohols with H2as Sole Reductant

Catalytic carbon-carbon bond formation building on reductive coupling is a powerful method for the preparation of organic compounds. The identification of environmentally benign reductants is key for establishing an efficient reductive coupling reaction. Herein an efficient strategy enabling H2 as the sole reductant for the palladium-catalyzed allyl-allyl reductive coupling reaction is described. A wide range of allylamines and allylic alcohols as well as allylic ethers proceed smoothly to deliver the C-C coupling products under 1 atm of H2. Kinetic studies suggested that the dinuclear palladium species was involved in the catalytic cycle.

Reaction of Phenyl-substituted Allyl-lithiums with Secondary Alkyl Halides. A Polar Process versus Single-electron Transfer

The reaction of 1-phenylallyl-lithium (1a) with optically active 2-halobutanes in ether in the presence of tetramethylethylenediamine or hexamethylphosphoramide gives exclusively 4-methyl-3-phenylhex-1-ene (5a) (coupling at the phenyl-substituted site) with essentially 100percent inversion of configuration.In contrast, treatment of 1,1-diphenylallyl-lithium (1b) with (-)-2-halobutanes under the same conditions results in the formation of a mixture of 4-methyl-3,3-diphenylhex-1-ene (5b) (coupling at C-1) and 4-methyl-1,1-diphenylhex-1-ene (6b) (coupling) at C-3).Moreover, C-C bond formation at the 1-position to provide (5b) is also found to proceed with complete inversionof configuration, while a small but significant loss of stereochemical integrity is observed in the case of the C-3 attack product (6b).These results suggest that a polar pathway should predominate for the formation of the C-1 attack products (5a,b), while competition between polar and single-electron-transfer processes occurs for the formation of the C-3 attack product (6b).

Reaction of Phenyl-Substituted Allyllithiums with tert-Alkyl Bromides. Remarkable Difference in the Alkylation Regiochemistry between a Polar Process and the One Involving Single-Electron Transfer

The reaction of phenyl-substituted allyllithiums 1a-h with tert-alkyl bromides was investigated systematically.The alkylation regiochemistry was influenced in a complicated fashion by various factors including substituent effects, both steric and electronic, solvents, and the presence of strongly coordinating additives, tetramethylethylenediamine and hexamethylphosphoramide.On the basis of the cyclizable probe experiments, the observed regiochemistry was interpreted as follows. (a) The reaction proceeds by two alternative pathways, a polar one and single electron transfer (SET), the extent of each path being influenced by the variable factors and (b) a polar pathway favors coupling at the phenyl-substituted site (C-1), while in the case of SET the C-C bond formation occurs predominantly at the site far from the phenyl substituent (C-3).

PALLADIUM-CATALYZED COUPLING OF ALLYLIC ACETATES WITH ZINC

Allylic acetates were coupled with zinc dust in the presence of a catalytic amount of to give the corresponding 1,5-dienes under mild conditions in high yields.Significant cosolvent effects were found with methanol or 1,2-ethanediol in tetrahydrofuran.