2415-91-0

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 17876-99-2 (4-chlorobenzyl)trimethylsilane 
• 589-15-1 1-bromomethyl-4-bromobenzene 
• 17095-20-4 p-<(trimethylsilyl)methyl>bromobenzene 
• 3728-43-6 p-(trimethylsilyl)toluene 
• 104-83-6 1-Chloro-4-(chloromethyl)benzene 

Downstream Products

• 22364-51-8 p-Trimethylsilylphenyl-trimethylsilylketon 
• 2004-89-9 4-Trimethylsilylmethyl-benzolsulfonsaeure-trimethylsilylester 
• 57337-80-1 (4-Methoxymethyl-phenyl)-trimethyl-silane 
• 1899-92-9 4-(trimethylsilanyl-methyl)-benzenesulfonic acid 

Relevant academic research and scientific papers

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.

DTBB-catalysed lithiation of chlorinated benzylic chlorides, alcohols, thiols or amines

The reaction of chlorinated benzyl chlorides (I) with an excess of lithium powder and a catalytic amount of DTBB (4 mol %) in the presence of different electrophiles [Pr(i)CHO, Bu(t)CHO, Et2CO, (CH2)5CO, PhCOMe, Me3/

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.

Lithiated benzyllithiums from chlorobenzyl chlorides by a DTBB-catalysed lithiation

The reaction of 2-, 3- or 4-chlorobenzyl chlorides (1a-c) with an excess of lithium and a catalytic amount of DTBB (7 mol%) in the presence of different electrophiles [Pr(i)CHO, Bu(t)CHO, Et2CO, (CH2)5CO, PhCOMe, Me3SiCl] in THF at -50°C leads after hydrolysis with water, to the expected dioles or disilylated compounds 2aa-2cf.