112245-94-0

Upstream product

• 74-90-8 hydrogen cyanide 
• 16051-42-6 (+/-)-threo-2,6-dihydroxy-4-(2-hydroxy-1-methylpropyl)-3-methylbenzoic acid 
• 16051-39-1 (+/-)-threo-(3,5-dihydroxy-2-methyphenyl)butan-2-ol (phenol B) 
• 79755-60-5 (+/-)-threo-3-(3,5-dimethoxy-2-methyl-phenyl)-butan-2-ol 
• 110087-15-5 (+/-)-threo-2-(2-hydroxy-1-methylpropyl)-4,6-dimethoxybenzoate 
• 110087-16-6 ethyl (+/-)-2,4-dimethoxy-6-(1-methyl-2-oxopropyl)benzoate 
• 100560-67-6 (+/-)-threo-3,4-dihydro-6,8-dimethoxy-3,4-dimethyl-1H-2-benzopyran-1-one 
• 110087-19-9 (+/-)-threo-3,4-dihydro-6,8-dimethoxy-3,4-dimethyl-1H-2-benzopyran 
• 122-51-0 orthoformic acid triethyl ester 
• 92120-69-9 ethyl 2-ethyl-4,6-dimethoxybenzoate 

Downstream Products

• 518-75-2 citrinin 
• 79755-67-2 3-<3,5-bis-(β-methoxyethoxymethoxy)-2-methylphenyl>butan-2-ol 
• 79755-71-8 2-<1-(3,5-dimethoxy-2-methylphenyl)ethyl>-2-methyl-1,3-dithiolan 
• 79755-70-7 2-<1-(3,5-dihydroxy-2-methylphenyl)ethyl>-2-methyl-1,3-dithiolan 
• 19492-33-2 3-(3,5-dihydroxy-2-methylphenyl)butan-2-one 
• 20186-01-0 5-((1R,2S)-2-Hydroxy-1-methyl-propyl)-2,4-dimethyl-benzene-1,3-diol 
• 112245-93-9 2,6-dihydroxy-4-((1R,2S)-2-hydroxy-1-methyl-propyl)-3-methyl-benzoic acid 

Relevant academic research and scientific papers

Enantioselective Synthesis of the Polyketide Antibiotic (3R,4S)-(-)-Citrinin

The fungal metabolite (-)-citrinin (1) was synthesized for the first time.Reaction of the Grignard reagent of 2,4-bis(benzyloxy)-6-bromotoluene (3) with (2S)-trans-(-)-2,3-dimethyloxirane (6) in the presence of 1,5-cyclooctadienecopper(I) chloride as catalyst leads to the formation of (2S,3S)-(-)-7 with erythro configuration.Compound (-)-7 could be transformed into (2R,3S)-(-)-9 with threo configuration via the formate (1R,2S)-(+)-8 by a Mitsunobu reaction.Reaction of the Grignard reagent of 3 with the achiral cis-2,3-dimethyl-oxirane yielded directly (+/-)-9.The starting material 3 was readily available from 1,3-bis(benzyloxy)-5-bromobenzene (4).Formylation of 4 furnished the aldehyde 5 which could be reduced to 3 with borane.Hydrogenolysis of the benzyl ether groups in (-)-9 gave (-)-2 with threo configuration.The remaining steps to produce citrinin from (-)-2 required carboxylation to 11, formylation and in situ ring closure with ethyl orthoformate to produce the required quinomethide structure.Application of the same reactions to (+/-)-9 and (+/-)-2 afforded (+/-)-citrinin in 40percent overall yield. - Key Words: Citrinin, (3R,4S)-(-)- / 2,3-Dimethyloxirane, trans-(-)- and cis- / Synthesis of erythro- and threo-3-arylbutan-2-ols

A Diastereoselective Synthesis of the Polyketide Antibiotic Citrinin using Toluate Anion Chemistry

The diastereoselectivity of various synthetic approaches to (+/-)-threo-3-(3,5-dihydroxy-2-methylphenyl)butan-2-ol ('Phenol B') (4), based on reactions of benzyl anions with electrophiles, has been investigated.The anion (9) derived from ethyl 2,4-dimethoxy-6-ethylbenzoate reacted with acetaldehyde to give mainly an erythro-product isolated as the lactone (12); acetylation with acetyl chloride to give a ketone, followed by reduction, gave mainly the required threo-lactone (11).An alternative route was frustrated by decomposition of the benzyl anion derived from 3,4-dihydro-6,8-dimethoxy-3-methyl-1H-2-benzopyran-1-one (17).Reduction of the carbonyl group of the threo-lactone (11) to a methyl gave the dimethyl ether of 'Phenol B', which was converted into (+/-)-citrinin (1).