39599-18-3

Reaction of methyl 3-acetoxy-2-methylenealkanoates with the reducing agent, lithium aluminium hydride (LAH): ethanol (1:1), provides (2E)-2-methylalk-2-en-1-ols, whereas, reaction of 3-acetoxy-2-methylenealkanenitriles with the same reagent provides (2Z)-2-methylalk-2-enenitriles in high yields.

Enone cyanohydrin diethyl phosphates reaced regio- and stereo-selectively with a variety of organocopper reagents to give γ-coupling products, (Z)-predominant alk-2-enenitriles.The methodology was applied to the synthesis of (+/-)-nuciferal, (+/-)-(E)- an

3-Buten-2-one cyanohydrin diethyl phosphate reacted regio- and stereo-selectively with a variety of dialkyl cuprates and ethoxycarbonylmethylcopper giving γ-coupling products, 2-alkene nitriles, one of which was used to synthesize (+/-)-(E)-Nuciferol.Keyw

The Mislow-Evans rearrangement of α,β- and α,γ-disubstituted allylic sulfoxides (2) to (E)-allylic alcohols (4) was found to occur under acidic conditions.By combination of this method with a catalytic oxidation of allylic sulfides (1), a novel one-pot tr

Novel and facile terminal trans-allylic and internal allylic oxidations of the gem-dimethyl olefin terminus of the terpenoids (1) are described which take place site-, regio-, and stereo-specificially via the same intermediate adduct between benzenesulphenyl chloride and (1).By this method, the allylic oxygenated terpenes (+/-)-nuciferal (11), (+/-)-ar-turmerone (12), (+/-)-ipsdienol (3c), neotorreyol (2e), (+/-)-6-hydroxydendrolasin (3e), and 6-oxodendrolasin (14) were synthesized.

To direct the aldolisation reaction in such a way that an aldehyde reacts upon the electrophilic carbonyl group of a ketone or of another aldehyde, it is necessary to mask the aldehyde and to transform it into a nucleophile.The present article presents an approach to this problem concerning unsaturated aldehydes and describes the condensation between the α-carbanion of acrolein and several carbonyl compounds. Aldol condensation at -70 degC, between 1,1-diethoxy-2-lithio-2-propene and several aldehydes leads to β-hydroxy-α-methylene acetals.These secondary allylic alcohols are stereoselectively transformed into trisubstituted functionalised olefinic compounds (Z-α-chlormethyl-α,β-unsaturated aldehydes and E-α-methyl-α,β-unsaturated primary alcohols). This method is illustrated by the syntheses of (+/-)-Z-chloronuciferal and (+/-)-E-nuciferol.