115377-36-1

Upstream product

• 60699-32-3 (E)-3,7-dimethylocta-2,6-dien-1-yl diethyl phosphate 
• 100-52-7 benzaldehyde 
• 5389-87-7 1-chloro-3,7-dimethylocta-2,6-diene 
• 6138-90-5 trans-geranyl bromide 
• 67883-63-0 (E)-3,7-dimethyl-1-tributylstannylocta-2,6-diene 
• 35266-82-1 (E)-((3,7-dimethylocta-2,6-dien-1-yl)oxy)benzene 
• 106-24-1 Geraniol 
• 20536-36-1 neryl chloride 

Relevant academic research and scientific papers

Effect of Crown Ethers on the Regioselectivity of Allylation of Benzaldehyde with Allylic Barium Reagents

An increase of α-regioselectivity was observed in the reaction of allylic barium reagents with aldehydes employing crown ether as an additive. For example, an α/γ regioselectivity was improved to 98/2 from 92/8, when an equimolar amount of 18-crown-6 was added to geranylbarium reagent in THF at -78°C prior to the reaction with benzaldehyde.

Forging C-C Bonds with Hindered Nucleophiles and Carbonyl Electrophiles: Reactivity and Selectivity of Allylic Tin Reagents/n-BuLi

Under activation with n-BuLi, trialkylstannanes containing crotyl-, geranyl-, and phenyldienylmethyl appendages were reacted with efficiency and selectivity to various ketone and enone electrophiles with low reactivity. The straightforward process gives access to tertiary alcohols that are vicinal to quaternary carbons. With α,α′-dimethoxy-γ-pyrone, on the other hand, the grafting of a dienyl side chain was effected to prepare dienyl α′-methoxy-γ-pyrone in a stereo- and regioselective and convergent manner. Furthermore, the advantages of this route were highlighted for the preparation of organolithium species at low temperature with the formation of a minimum amount of salts. Synthetic manipulations were demonstrated to illustrate the potential of the chemistry for constructing acyclic and cyclic terpene scaffolds.

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).

Allylic Phosphates as Allyl Anion Synthons. Lithium-induced Allylation of Carbonyl Compounds

Ultrasonication of allylic phosphates and carbonyl compounds with a lithium powder gave high yields of the corresponding homoallylic alcohols.