78522-84-6

Upstream product

• 109-65-9 1-bromo-butane 
• 538-86-3 benzyl methyl ether 
• 109-72-8 n-butyllithium 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 67-56-1 methanol 
• 1009-14-9 phenyl butyl ketone 

Downstream Products

• 1726-12-1 1,1-diphenylpentane 

Relevant academic research and scientific papers

Highly chemoselective lithium metal reductions of benzaldehyde bis(2-methoxyethyl) acetals

Naphthalene-catalysed reductions of PhCH(OR)2 (R = Me, CH2CH2OMe) acetals by lithium metal, followed by reactions with electrophiles (H+, TMSCl, nBuBr, CH2=CHCH2Br), proceed with high chemoselectivity when the reductions are carried out at -90 °C especially for R = CH2CH2OMe. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany 2002.

Asymmetric nucleophilic substitution of acetals

Benzaldehyde dimethylacetal (1) and 2-aryl-1,3-dioxolanes 5 react with organolithium reagents 2 in the presence of chiral ligands such as sparteine (3), 1-alkoxy-2-aminoethanes, or 1,2-dialkoxyethanes and BF3 to afford monosubstitution products in high yields and in up to 81% enantiomeric excess. The enantioselectivity is strongly influenced by steric effects in the acetal and in the reagent. The highest ee was achieved with 2-(2-isopropyl)-1,3-dioxolane (5c) on treatment with 2-ethylphenyllithium (2i) in the presence of sparteine. The approach was applied to the synthesis of enantioenriched (S)-(-)-neobenodine (17) with 49% ee.

Metalation of arylmethyl alkyl ethers

Arylmethyl alkyl ethers 1a-11 were metallated with n-BuLi or sec-BuLi in THF at different temperatures, affording α-alkoxy-substituted arylmethyllithium derivatives. At low temperature, the organometallics derived from methyl and isopropyl ethers are suff

Synthesis of Functionalized Heteroaromatics: Application to Formal Total Synthesis of Camptothecin

The formal total synthesis of camptothecin was achieved via two types of lithiation reactions of pyridine derivatives and a Pd-catalyzed carbonylation of pyridylmethyl methanesulfonates.

Metalation of Arylmethyl Methyl Ethers and Connection with Their Reductive Electrophilic Substitution

Stable α-methoxy arylmethyl carbanions can be generated by metalation of arylmethyl methyl ethers, 1, with n-BuLi in THF at -40 degC, avoiding Wittig rearrengement to the corresponding alkoxides 2.Reaction of these carbanions with various electrophiles afforded the expected products 3 in satisfactory yields.Connection between the metalation procedure and the reductive electrophilic substitution of arylmethyl methyl ethers allowed the transformation of compounds 1 into 2-arylpropanoic acids, 5.

Single and double reductive cleavage of C-O bonds of aromatic dimethyl acetals and ketals: Generation of benzylic mono- and dicarbanions

The reductive cleavage of aromatic dimethyl acetals and ketals, 1, with Li metal in THF at low temperature allows the generation of stable α-alkoxy-α-arylsubstituted carbanions, avoiding the Wittig rearrangement. Reaction of these carbanions with various electrophiles afforded the expected products 2. Further in situ reaction of compounds 2 afforded the products of reductive electrophilic disubstitution, 3.

Photochemistry of Phenyl Alkyl Ketones in the Presence of Triphenylphosphine

Photolysis of butyrophenone, valerophenone, γ-methylvalerophenone, and acetophenone in methanol in the presence of triphenylphosphine gave triphenylphosphine oxide and 1-phenyl-1-methoxyalkanes in addition to the expected Norrish type II products.Kinetic studies of these photoreactions by steady-state measurements show that triplet-state ketones are quenched by Ph3P but that the corresponding biradicals do not interact with Ph3P.

Benzylic Substitution of Benzyl Methyl Ether

Treatment of benzyl methyl ether with n-butyl-lithium-tetramethylenediamine in hexane gave benzylic-lithiation, without ortho-lithiation or a Wittig type rearrangement.The benzylic-lithiated benzyl methyl ether was then allowed to react with benzophenone,