50987-46-7

Upstream product

• 74-88-4 methyl iodide 
• 67-56-1 methanol 
• 19687-18-4 acetic acid 3,5,5-trimethylcyclohex-2-enyl ester 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 
• 470-99-5 isophorol 
• 21195-62-0 3,5,5-Trimethyl-2-cyclohexenone tosylhydrazone 

Downstream Products

• 1219117-62-0 C₁₃H₂₅O₃PS 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 

Relevant academic research and scientific papers

Molybdenum(II)- and tungsten(II)-catalyzed allylic substitution

The molybdenum(II) complexes Mo(CO)5(OTf)2 (7a), [Mo(CO)4Br2]2 (8a), their tungsten(II) congeners 7b and 8b, and bimetallic complex Mo(CO)3(MeCN)2(SnCl3)Cl (9a) have been found to catalyze the C-C bond-forming allylic substitution with silyl enol ethers derived from β-dicarbonyls (e.g., 16 + 30 → 46) or from simple ketones (e.g., 16 + 32 → 50), aldehydes, and esters as nucleophiles under mild conditions (room temperature, 1-2 h). Methanol, as a prototype oxygen nucleophile, reacts in a similar fashion (e.g., 16 + MeOH → 43). Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.

Reaction of cyclic allylic acetates with aliphatic alcohols in the presence of cerium(III) chloride

The reactions of selected allylic acetates with methanol, ethanol, n-propyl alcohol, isopropyl alcohol and tert-butyl alcohol in the presence of catalytic amounts of cerium(III) chloride are described. Allylic alkyl ethers, bis-allylic ethers and 1,3-dienes were obtained depending on the structure of the acetates.

The reaction of cyclic allylic alcohols with aliphatic alcohols in the presence of cerium(III) chloride

Cyclic secondary and tertiary allylic alcohols react with primary aliphatic alcohols in the presence of cerium(III) chloride heptahydrate to give alkyl allylic ethers. When secondary or tertiary aliphatic alcohols are used 1,3-dienes are obtained from allylic alcohols heaving the 3-methyl-2-en-1-ol moiety (3-8, 13-15).

On the mechanism of alcoholysis of allylic and benzylic alcohols and of epoxides in the presence of ceric ammonium nitrate

The methanolysis of allylic alcohols, benzylic tertiary alcohols and epoxides in the presence of a catalytic amount of ceric ammonium nitrate (CAN) is shown to be catalysed by protons generated from the oxidation of methanol. This reaction is also catalysed by Lewis acids.

A Novel Methylation of Allylic Alcohols Using cis-Dichlorobis(triphenylphosphine)platinum(II)-Tin(II) Chloride Dihydrate Complex Catalyst

The reaction of allylic alcohols in benzene-methanol (3:2) solvent in the presence of cis-dichlorobis(triphenylphosphine)platinum(II)-tin(II) chloride dihydrate complex catalyst afforded allylic methyl ethers.The structure of the obtained compounds was identified by direct comparison with authentic sample.Cholest-4-en-3α-ol, with a quasi-axial hydroxy group, gave a quantitative yield of 3α-methoxycholest-4-ene.On the other hand, cholest-4-en-3β-ol, with a guasi-equatorial hydroxy group, yielded 3β-methoxycholest-4-ene preferentially, but also yielded 3α-methoxycompound as a by-product, lowering the selectivity of the reaction.

Synthesis of Alkyl Allylic Ethers and 1,3-Dienes by the Reaction of Conjugated Cyclohexenones with Sodium Borohydride-Cerium(III) Chloride in Aliphatic Alcohols

The reaction of conjugated cyclohexenones 1,3-containing 3-methyl-2-en-1-one moiety with NaBH4/CeCl3*7H2O in primary aliphatic alcohols (MeOH, EtOH, n-PrOH) affords alkyl allylic ethers and 1,3-dienes.In isopropanol or tert-butanol only 1,3-dienes are obtained.Ketones 4-6 containing 2-methyl-2-en-1-one moiety are reduced under the same conditions to the corresponding allylic alcohols irrespective of the alcohol used.Key words: reduction, α,β-unsaturated ketones, allylic alcohols, alkyl allylic ethers, sodium borohydride, cerium(III) chloride

Allylic Substitution Catalyzed by a New Molybdenum Complex

A new molybdenum(II) complex (E), generated in situ from Mo(CO)6 by sequential treatment with PhCH2(Et)3N+Cl- and CF3SO3Ag (3 equiv.), has been found to catalyze the substitution of allylic acetates with MeOH (4 -> 5 8; 9