2085-87-2

Upstream product

• 1067-44-3 ethoxymethyltributyltin 
• 98-86-2 acetophenone 
• 3188-13-4 ethyl chloromethyl ether 
• 64-17-5 ethanol 
• 98-83-9 isopropenylbenzene 
• 15561-33-8 1-chloro-2-phenylpropan-2-ol 

Downstream Products

• 104681-83-6 1-Methoxy-3-phenyl-butan-2-ol 
• 104681-83-6 1-Methoxy-3-phenyl-butan-2-ol 
• 34713-70-7 2-Phenylpropanal 
• 7534-41-0 ethyl-(2-phenyl-allyl)-ether 

Relevant academic research and scientific papers

4,4′-Di-tert-butylbiphenyl-catalysed lithiation of chloromethyl ethyl ether: A barbier-type new and easy alternative to ethyl lithiomethyl ether

The reaction of an equimolar amount of chloromethyl ethyl ether (1) and different carbonyl compounds (2) with an excess of lithium powder (1:7 molar ratio) in the presence of a catalytic amount of 4,4′-di-tert-butylbiphenyl (5 mol %) in THF at 0°C leads, after hydrolysis, to the corresponding hydroxyethers 3.

Visible light-promoted dihydroxylation of styrenes with water and dioxygen

An efficient visible light promoted metal-free dihydroxylation of styrenes with water and dioxygen has been developed for the construction of vicinal alcohols. The protocol was operationally simple with a broad substrate scope. The mechanistic studies demonstrated that one of the hydroxyl groups came from water and the other one came from molecular oxygen. Additionally, the β-alkyoxy alcohols could also be obtained using a similar strategy.

Lithiation reactions catalyzed by linear and cross-linked arene-based polymers. Generation of functionalized organolithium compounds

Lithiation of various substrates, such as chlorinated acetals, α-chloro ether, dichloro derivatives benzo-fused heterocycles, and allyl and benzyl derivatives, with excess lithium powder in the presence of a catalytic amount of soluble linear or insoluble cross-linked arene (naphthalene or biphenyl)-based polymers yields the expected organolithium intermediates. The latter react with electrophiles either in two steps or under Barbier-type reaction conditions to afford the corresponding adducts. The catalyst is easily recuperated by filtration at the end of the process, and the procedure can be regarded as a reasonable alternative to the use of free arenes as electron carrier in lithiation reactions.

Polyphenylene as an electron transfer catalyst in lithiation processes

The lithiation of different functionalised chlorinated materials (1a-c), dichlorinated compounds (1d-f) and benzofused cyclic ethers (1g,h) with lithium powder in the presence of catalytic amounts of either linear (LPP) or crosslinked (CPP) polyphenylene, in THF at temperatures ranging between -78 and 20°C, leads to the expected organolithium intermediates (Ia-h), which by reaction with electrophiles [ButCHO, PhCHO, Et2CO, (CH2)5CO, PhCOMe, Me3SiCl] gives, after hydrolysis with water, the expected products 2aa-hf.

Polymer supported arene-catalysed lithiation reactions

The reaction of functionalised mono or dichlorinated materials 1a-6a with an excess of lithium and a catalytic amount of a naphthalene (P(N)) or biphenyl (P(B)) supported polymer (easily prepared by radical copolymerisation of 2-vinylnaphthalene or 4-vinylbiphenyl with vinylbenzene and divinylbenzene) in THF either in the presence or not of different electrophiles [Me3SiCl, (i)prCHO, PhCHO, Et2CO, (CH2)4CO, (CH2)5CO, (c- C3H5)2CO, (i)Pr2CO, PhCOMe, PhCH=NPh] at -78 or -50°C leads, after hydrolysis with water, to the expected functionalised products 1ca-6ck. The polymeric catalyst is quantitatively recovered and can reused several times without any loss of activity.

Polymer supported naphthalene-catalysed lithiation reactions

The reaction of functionalised mono or dichlorinated materials 1a-6a with an excess of lithium and a catalytic amount of a naphthalene supported polymer (P-152, easily prepared by radical copolymerisation of 2-vinylnaphthalene, styrene and divinylbenzene) in THF either in the presence (Barbier-type conditions) or not of different electrophiles [Me3SiCl, Bu(n)CHO, Bu(i)CHO, PhCHO, Et2CO, c(C3H5)2CO, Pr(i)2CO, (CH2)4CO, (CH2)5CO, PhCOMe, PhCH=NPh] leads, after hydrolysis, to the expected products 1c-6c. The catalyst is quantitatively recovered and can be reused several times without any loss of its activity.

Lithiomethyl ethyl ether from chloromethyl ethyl ether via a DTBB-catalysed lithiation

The reaction of equimolar amounts of chloromethyl ethyl ether (1) and a carbonyl compound [Bu(n)CHO, Bu(t)CHO, PhCHO, Pr(i)2CO, Bu(t)2CO, (CH2)4CO, 2-cyclohexenone, PhCOMe] with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in THF at 0°C (Method A) leads, after hydrolysis, to the corresponding hydroxyethers 2. The reaction can be also carried out in a two-step process: tandem lithiation at -90°C and reaction with the electrophile [Bu(n)CHO,(CH2)4CO, PhCOMe, PhMe2SiCl, CO2, PhCN, PhCONMe2, CyNCO, PhN=CHPh] at -90 to -60°C (Method B).

Alcoxymethyltributyletains precurseurs d'alcoxymethyllithiums: application a la synthese de monoethers d'α-glycols et a l'homologation de cetones en aldehydes

Ethoxymethyltributyltin (obtained from diethoxymethyltributyltin, acetyl chloride and tributyltin hydride) and methoxymethyltributyltin (obtained from chloromethyl-methyl ether and tributylstannylmagnesium chloride) have been transmetallated with butyllithium to give the corresponding alkoxymethyl lithium reagents.This reaction, although usually performed in ether, is possible in a variety of other solvents thus simplifying some of the problems encountered during isolation of the products.The alkoxymethyllithiums obtained react with aldehydes and ketones to give cleanly the corresponding monoprotected α-glycols.Stereochemical trends were observed for hydratropaldehyde and 4-tertiarybutylcyclohexanone, while regiochemical trends were evaluated in the case of cyclohexen-2-one.Syntheis of aldehydes has been achieved in good yields from tertiary monoprotected α-glycols using conventional methods.