63213-06-9

Upstream product

• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 2259-30-5 tert-butylmagnesium bromide 
• 507-20-0 tertiary butyl chloride 
• 131131-39-0 3-phenylpropen-1-yl magnesium chloride 
• 507-19-7 t-butyl bromide 
• 64740-46-1 1-lithio-3-phenylpropane 
• 34041-44-6 1-phenylpropenyl-lithium 
• 87802-71-9 (E)-methyl cinnamyl carbonate 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 

Relevant academic research and scientific papers

Nickel-Catalyzed Reductive Allylation of Tertiary Alkyl Halides with Allylic Carbonates

The construction of all C(sp3) quaternary centers has been successfully achieved under Ni-catalyzed cross-electrophile coupling of allylic carbonates with unactivated tertiary alkyl halides. For allylic carbonates bearing C1 or C3 substituents, the reaction affords excellent regioselectivity through the addition of alkyl groups to the unsubstituted allylic carbon terminus. The allylic alkylation method also exhibits excellent functional-group compatibility, and delivers the products with high E selectivity.

Cross-Coupling Reaction of tert-Alkyl halides with Grignard Reagents in Dichloromethane as a Non-Lewis Basic Medium

In dichloromethane as a non-Lewis basic solvent, 1-haloadamantane 1 underwent a cross-coupling reaction with Grignard reagents to give bridgehead-substituted products 3-16 in moderate yields.In this case the same kind of halogen in both 1 and a Grignard reagent was favored; if not, functional exchange (i.e., 1a to 1c) occurred first.The reaction using 5-hexenylmagnesium bromide as a radical probe afforded uncyclized/cyclized coupling products in a 6/4 ratio.These fact suggested the significant participation of the single-electron-transfer process in these reactions.The present method could be extended to tert-butylation with some Grignard reagents.Interestingly, 1,3-dichloro-3-methylbutane coupled with butylmagnesium chloride selectively at the tertiary position. for the above displacement reaction of 1, an organozinc was also found to be effective.

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).

Reaction of 1-Aryl-3-chloropropenes with Grignard Reagents. Nucleophilic Substitution versus Single-electron Transfer

The reactions of ambident 1-aryl-3-chloropropenes (1a-e) with a series of Grignard reagents, R'MgY (R' = Me, Pr, Ph, Pri, But; Y = Br, I), were carried out in diethyl ether (EE) and tetrahydrofuran (THF).The products were a mixture of two alkylation products (2) and (3), and three dimerization products (4)-(6).The alkylation:dimerization ratio and the composition of the two alkylation products were a marked function of substituent electronic effects in the chlorides (1a-e), R' or Y of R'MgY, and solvent.On the basis of the stereochemistry of alkylation, cyclizable probe experiments, and the effect of the addition of FeCl3 on product composition, the following conclusions were obtained.First, dimers (4)-(6) are most likely to be produced by a mechanism involving single-electron transfer (SET).Second, for the formation of alkylation products (2) and (3), three alternative pathways contribute depending on the nature of R'MgY and solvent, (a) competitive SN2-SN2' pathways in the reaction of R'MgBr in EE, (b) a process involving SET in the reaction with R'MgI in EE, and (c) SN2 pathways in the reaction of R'MgBr in THF.

Reaction of 1-Arylpropenyl-lithium with t-Alkyl Bromides. The Influence of Substituent Electronic Effects and Additives on the Course of the Reaction

The reaction of 1-arylpropenyl-lithium (1a-c) with t-alkyl bromides proceeds by either a nucleophilic substitution or single electron transfer mechanism, the preferred pathway being a function of electronic substituent effects and the absence or presence of tetramethylethylenediamine or hexamethylphosphoramide.