98369-87-0

Upstream product

• 930-68-7 cyclohexenone 
• 5925-78-0 benzyl methyl selenide 
• 100-44-7 benzyl chloride 
• 6921-34-2 benzylmagnesium chloride 

Relevant academic research and scientific papers

Guanidine–Copper Complex Catalyzed Allylic Borylation for the Enantioconvergent Synthesis of Tertiary Cyclic Allylboronates

An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine–copper catalyst. The allylboronates were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities (up to 99 % ee), and could be further transformed into diverse functionalized allylic compounds without erosion of optical purity. Experimental and DFT mechanistic studies support an SN2′ borylation process catalyzed by a monodentate guanidine–copper(I) complex that proceeds through a special direct enantioconvergent transformation mechanism.

Beryllium dichloride: Efficient promoter for the addition of organolithiums and organomagnesiums to cyclohexen-2-one

Organoberyllium compounds, generated by transmetallation from Grignard and organolithium reagents react with 2-cyclohexenone to give predominantly the adducts resulting from conjugated addition. The chemoselectivity of this reaction was found to be highly dependent upon the nature of organic moiety and of the conditions used.

Allylbarium reagents: Unprecedented regio- and stereoselective allylation reactions of carbonyl compounds

The first direct preparation of allylbarium reagents by reaction of in situ generated reactive barium with various allylic chlorides and their new and unexpected selective allylation reactions with carbonyl compounds are disclosed. Highly reactive barium was readily prepared by the reduction of barium iodide with 2 equiv of lithium biphenylide in dry THF at room temperature. A variety of carbonyl compounds reacted with barium reagents generated from (E)- or (Z)-allylic chlorides in THF at -78 °C. All reactions resulted in high yields with remarkable α-selectivities not only with aldehydes but also with ketones. The double bond geometry of the starting allylic chloride was completely retained in each case. Stereochemically homogeneous (E)- and (Z)-β,γ-unsaturated carboxylic acids were easily prepared in good yields by highly α-selective carboxylation of allylic barium reagents with carbon dioxide. A selective Michael addition reaction with α,β-unsaturated cycloalkanone was also achieved using an allylbarium reagent. Treatment of 2-cyclopentenone (1 equiv) with allylbarium chloride (2 equiv) in THF at -78 °C for 20 min afforded 3-allylcyclopentanone in 94% yield with a 1,4/1,2 ratio of >99/1. Furthermore, the in situ generated barium enolate was efficiently trapped with various kinds of electrophiles (Me2C=CHCH2Br, nC5H11CHO, and CH3COCl).

NOVEL SYNTHESIS OF BENZYLLITHIUMS FROM BENZYLSELENIDES

Benzylselenides are found to be valuable precursors of benzyllithiums.The scope of the new method is disclosed.