113365-21-2

Upstream product

• 591-51-5 phenyllithium 
• 177859-18-6 1-[(3-Methyl-but-2-enyloxy)-phenyl-methyl]-1H-benzotriazole 
• 119-61-9 benzophenone 
• 870-63-3 prenyl bromide 
• 100-52-7 benzaldehyde 
• 17314-40-8 3-Methyl-2-butenyl-trimethylstannane 

Downstream Products

• 108970-09-8 (E)-3-Hydroxy-4,4-dimethyl-1-phenyl-1,5-hexadiene 
• 71787-60-5 4,4-dimethyl-1-phenyl-hex-5-en-3-ol 
• 27644-02-6 2,2-dimethyl-1-phenylbut-3-en-1-ol 
• 124154-59-2 2,2-dimethyl-1-(4-methoxyphenyl)-3-buten-1-ol 

Relevant academic research and scientific papers

Photocatalytic Barbier reaction-visible-light induced allylation and benzylation of aldehydes and ketones

We report a photocatalytic version of the Barbier type reaction using readily available allyl or benzyl bromides and aromatic aldehydes or ketones as starting materials to generate allylic or benzylic alcohols. The reaction proceeds at room temperature under visible light irradiation with the organic dye 3,7-di(4-biphenyl)1-naphthalene-10-phenoxazine as a photocatalyst and DIPEA as sacrificial electron donor. The proposed cross-coupling mechanism of a ketyl- and an allyl or benzyl radical is supported by spectroscopic investigations and cyclic voltammetry measurements.

Benzotriazole-mediated [2,3]-wittig rearrangement. General and stereocontrolled syntheses of homoallyl alcohols and β,γ-unsaturated ketones

Readily accessible allyl 1-(benzotriazol-1-yl)alkyl ethers (13 and 19), upon treatment with 2.5 equiv of nucleophilic lithium reagents, give secondary and tertiary homoallyl alcohols (16 and 21), respectively, exclusively in the E configuration in excellent yields. This is achieved by deprotonation followed by [2,3]-Wittig rearrangement, departure of the benzotriazolyl group, and then nucleophilic addition to the resulting carbonyl compound. Following a similar protocol, primary E-homoallyl alcohols 18 are prepared in good yield by the reaction of ethers 13 with LDA in the presence of NaBH4. Our approach complements the stereochemical Z-selective syntheses of primary homoallyl alcohols of Still and of Bruckner. Wittig rearrangement of the anions of 19 generated with LDA analogously furnishes E-β,γ-unsaturated ketones 20 in excellent yields.

Photoinduced Allylation of Aromatic Carbonyl Compounds by Allylic Stannanes

irradiation of aromatic carbonyl compounds and allyl-, 2-methyl-2-propenyl, or 3-methyl-2-butenyltrimethylstannanes in acetonitrile afforded δ,γ-unsaturated alcohols as major product.A photoinduced electron transfer mechanism is proposed for the allylations.