288301-41-7

Upstream product

• 94-66-6 2-allylcyclohexan-1-one 
• 292638-85-8 acrylic acid methyl ester 
• 108-94-1 cyclohexanone 
• 35466-83-2 allyl methyl carbonate 
• 1596247-65-2 2-(trimethylsilyl)ethyl 1-(3-methoxy-3-oxopropyl)-2-oxocyclohexane-1-carboxylate 

Downstream Products

• 288301-44-0 (-)-3-[(1S)-4-oxo-1-(2-propenyl)-2-cyclohexenyl]propyl 2,2-dimethylpropanoate 
• 288301-43-9 (-)-3-[(1R)-1-(2-propenyl)-2-cyclohexenyl]propyl 2,2-dimethylpropanoate 
• 288301-53-1 (R)-2-Allyl-2-(3-hydroxy-propyl)-cyclohexanol 

Relevant academic research and scientific papers

Development of (trimethylsilyl)ethyl ester protected enolates and applications in palladium-catalyzed enantioselective allylic alkylation: Intermolecular cross-coupling of functionalized electrophiles

The development of (trimethylsilyl)ethyl ester protected enolates is reported. The application of this class of compounds in palladium-catalyzed asymmetric allylic alkylation is explored, yielding a variety of α-quaternary six- and seven-membered ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to traditional β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of (trimethylsilyl)ethyl β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Total Syntheses of (-)-Methyl Atis-16-en-19-oate, (-)-Methyl Kaur-16-en-19-oate, and (-)-Methyl Trachyloban-19-oate by a Combination of Palladium-Catalyzed Cycloalkenylation and Homoallyl-Homoallyl Radical Rearrangement

Asymmetric total syntheses of (-)-methyl atis-16-en-19-oate (1c), (-)-methyl kaur-16-en-19-oate (2c), and (-)-methyl trachyloban-19-oate (3c) have been achieved by employing a hybrid strategy of palladium-catalyzed cycloalkenylation and homoallyl-homoallyl radical rearrangement. The common synthetic intermediate 5 was prepared from 2-allylcyclohexanone (4) with 98% ee using d'Angelo's asymmetric Michael addition. A series of functional group modifications in 5 via palladium-catalyzed cycloalkenylation led to (+)-14, which had already been prepared by us as racemate. (-)-Methyl atis-16-ene-19-oate (1c) was generated via homoallyl-homoallyl radical rearrangement. On the other hand, Wolff-Kishner reduction of 18 followed by esterification yielded (-)-methyl kaur-16-en-19-oate (2c) together with (-)-methyl trachyloban-19-oate (3c).