50987-46-7Relevant articles and documents
Molybdenum(II)- and tungsten(II)-catalyzed allylic substitution
Malkov, Andrei V.,Baxendale, Ian R.,Dvorak, Dalimil,Mansfield, Darren J.,Kocovsky, Pavel
, p. 2737 - 2750 (2007/10/03)
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.
The reaction of cyclic allylic alcohols with aliphatic alcohols in the presence of cerium(III) chloride
Uzarewicz,Dresler
, p. 181 - 195 (2007/10/03)
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).
A Novel Methylation of Allylic Alcohols Using cis-Dichlorobis(triphenylphosphine)platinum(II)-Tin(II) Chloride Dihydrate Complex Catalyst
Sakamaki, Hiroshi,Kameda, Noriyuki,Iwadare, Tsukasa,Ichinohe, Yoshiyuki
, p. 3491 - 3496 (2007/10/03)
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.