42463-79-6Relevant academic research and scientific papers
Synthesis of (+)- and (-)-gossonorol and cyclisation to boivinianin B
Abecassis, Keren,Gibson, Susan E.
experimental part, p. 2938 - 2944 (2010/08/07)
The first enantioselective synthesis of gossonorol has been achieved in good overall yield and excellent enantioselectivity, demonstrating the utility of a novel approach to enantiopure tertiary benzylic alcohols. Epoxidation of enantiopure gossonorol followed by acid-catalysed cyclisation gave a diastereoisomeric mixture of boivinianin B, typical of the diastereoisomeric mixtures of this compound found in nature. Separation of the diastereoisomers and determination of their enantiopurity revealed that the stereochemical integrity of the benzylic alcohol of gossonorol had been preserved during the epoxidation/cyclisation reaction.
Lanthanide(III) triflate-catalyzed thermal- and microwave-assisted synthesis of benzyl ethers from benzyl alcohols
Handlon, Anthony L.,Guo, Yu
, p. 111 - 114 (2007/10/03)
The lanthanide(III) trifluoromethanesulfonate-catalyzed condensation of benzyl alcohols with primary and secondary alcohols is described. This reaction proceeds readily with benzyl alcohols that have an alkyl or aryl substituent at the α-, ortho-, or para-position using microwave radiation or heating. The intra-molecular variant of this reaction leads to cyclic benzofurans.
REACTIVITY OF 3,6-DIMETHOXY-3,6-DIMETHYLCYCLOHEXA-1,4-DIENE: NUCLEAR VERSUS BENZYLIC NUCLEOPHILIC SUBSTITUTION
Alonso, Francisco,Barba, Isidoro,Yus, Miguel
, p. 2069 - 2080 (2007/10/02)
The treatment of cis/trans-3,6-dimethoxy-3,6-dimethylcyclohexa-1,4-diene (ca. 1/1 mixture; easily prepared electrochemically in multigram scale from p-xylene) under acidic conditions (acetic, trifluoroacetic, sulfuric, or a Lewis acid) yields almost exclusively 2-methoxy-1,4-dimethylbenzene 4, through a trasposition reaction.The use of aqueous hydrochloric or hydrofluoric acid gives 2,5-dimethylphenol 12, and with hydrogen chloride a mixture of 2- and α-chloro-p-xylene (13, 14) is isolated.Different oxygen-, nitrogen-, and sulfur-containing nucleophiles (alcohols,thiols, or hydrazoic acid) react with 3 under acid catalysis giving the corresponding products resulting from a nuclear or/ and benzylic substitution on p-xylene (15 - 20).The reaction of compound 3 with organolithium reagents affords exclusively benzylic products 21 in a regiospecific manner.In all cases the mixtures of isomers are separated by column chromatography.The lithiation of compound 3 with lithium powder or lithium naphthalenide fails, giving p-xylene.A probable mechanism is proposed for the studied reactions.
