154807-80-4

Upstream product

• 637-69-4 4-Methoxystyrene 
• 75400-50-9 9-[2-(4-methoxy-phenyl)-ethyl]-9-bora-bicyclo[3.3.1]nonane 
• 5406-18-8 3-(p-methoxyphenyl)-1-propanol 
• 20401-88-1 3-(4-methoxyphenyl)propional 
• 154807-78-0 Ethyl 2-methyl-5-(4-methoxyphenyl)-2(E)-pentenoate 

Downstream Products

• 154807-81-5 1-Bromo-5-(4-methoxyphenyl)-2-methyl-2-pentene 
• 130749-50-7 (E)-6-(4-methoxyphenyl)-3-methylhex-3-en-1-ol 
• 154807-85-9 (1S,4aR,10aS)-6-Methoxy-1,4a-dimethyl-2-oxo-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene-1-carboxylic acid (1S,2R,5S)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 154903-59-0 (1R,4aS,10aR)-6-Methoxy-1,4a-dimethyl-2-oxo-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene-1-carboxylic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 154807-86-0 (1R,4aR,10aS)-6-Methoxy-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene-1-carboxylic acid (1S,2R,5S)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester 
• 154903-60-3 (-)-Phenylmenthyl (+)-O-methylpodocarpate 
• 10037-26-0 O-methylpodocarpic acid 
• 16826-86-1 12-O-methylpodocarpol 
• 16826-83-8 12-O-methylpodocarpal 

Relevant academic research and scientific papers

Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement

A gold(I)-catalyzed enantioselective thioallylation of propiolates with allyl sulfides is described. The key mechanistic element is a sulfonium-induced Claisen rearrangement which helps minimize the allyl dissociation and render higher enantioselectivity. This protocol features remarkable scope of the allyl moiety, allowing enantiocontrolled synthesis of all-carbon quaternary centers, and exhibits exceptional functional group compatibility with many Lewis bases and π-bonds. This intermolecular variant of Claisen rearrangement forges both C-S and C-C bonds concomitantly, providing efficient access to interesting optically active organosulfur compounds which can be transformed further through the vinyl sulfide as a functional handle. The rate of the reaction was zeroth order with respect to allyl sulfides, which suggested a reversible inhibition, providing a resting state for the catalyst. The Hammett plot displayed a correlation with σp values, suggesting a turnover-limiting sigmatropic rearrangement where decreased electron-density on sulfur accelerated the rearrangement.

Asymmetric Induction in Mn(III)-Based Oxidative Free-Radical Cyclizations of Phenylmenthyl Acetoacetates and 2,5-Dimethylpyrrolidine Acetoacetamides

Mn(III)-based oxidative free-radical cyclization of phenylmenthyl ester 1e afforded 90percent of 13 with 86percent de.Cyclization of 31b provided 56percent of (+)-podocarpic acid precursor 32e with 82percent de.The direction of de was opposite in these two cases.Oxidative cyclization of α-methyl β-keto ester 44b gave a 1:1.6 mixture of 46b and 47b while α-propyl β-keto ester 44d produced a >10:1 mixture of 46d and 47d indicating that the extent and direction of de is dependent on the size of the α-substituent.The reaction proceeds through transition states 12 and 56 with large α-substituents and through transition states 19 and 57 with small α-substituents.The de depends on the double-bond substitution pattern as shown by the decreased de with 37b and 37d, and selectivity in the 5-exo cyclization of 64b, 65b, 70b, and 71b is low.