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Upstream product

• 52752-16-6 2,2-diethoxybutane 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 673-32-5 1-Phenylprop-1-yne 
• 10191-25-0 3-oxo-valeric acid 
• 78761-38-3 ethyl (E)-cinnamyl propionate 
• 741262-35-1 (E)-3-phenylprop-2-en-1-yl 3-oxopentanoate 
• 87012-79-1 2-(trans-cinnamyloxy)-1-butene 

Relevant academic research and scientific papers

Tandem Rh-catalysis: Decarboxylative β-keto acid and alkyne cross-coupling

Herein, we describe a regioselective Rh-catalyzed decarboxylative cross-coupling of β-keto acids and alkynes to access branched γ,δ-unsaturated ketones. Rh-hydride catalysis enables the isomerization of an alkyne to generate a metal-allyl species that can undergo carbon-carbon bond formation. Ketones are generated under mild conditions, without the need for base or activated electrophiles.

Ruthenium-catalyzed decarboxylative allylation of nonstabilized ketone enolates

(Matrix Presented) Bipyridyl(pentamethylcyclopentadienyl)ruthenium chloride is an efficient catalyst for the formal [3,3] rearrangement of allyl β-ketoesters. The mechanism of the transformation involves formation of π-allyl ruthenium intermediates, which

Acyclic Stereoselection in the Ortho Ester Claisen Rearrangement

The ortho ester Claisen rearrangement of trisubstituted allylic alcohols exhibits significant levels of diastereoselection. In E allylic alcohols, a 1,3-diaxial interaction develops in the chairlike transition state leading to the anti isomer, rendering the reaction syn selective by a factor of 3-5 to 1. In Z allylic alcohols, the 1,3-diaxial interaction develops in the transition state leading to the syn isomer, generating an anti:syn selectivity of 6-15 to 1. The relative stereochemistry of the syn isomer was confirmed independently by the synthesis of the mycotoxin botryodiplodin.

Stereoselective Acid-Catalyzed Claisen Rearrangements

An alkyl substituent in the 2-position of an E trisubstituted allylic alcohol confers significant diastereoselectivity on ortho ester and ketal Claisen rearrangements of the system.

Ketal Claisen Rearrangements of Simple Aliphatic Ketals

The ketal Claisen rearrangement has been studied with eight simple unsymmetrical ketals in order to establish the regioselectivity associated with the transformation.Three different allylic alkohols were examined.Carbon-carbon bond formation on the more highly substituted branch of the parent ketone generally predominated over substitution on the less highly substituted branch.However, additional substituents on the α or β carbons of the ketal lower the selectivity substantially.Extensive β substitution can completely reverse the normal selectivity.The rection is relatively insensitive to the concentration of the weak acid catalyst.The yields range between 27 and 84 percent, and the products have been characterized.A model that accounts for the observations is also described.

Regioselectivity of the Ketal Claisen Rearrangement

The ketal Claisen rearrangement with a simple unsymmetrical ketal exhibits a high degree of regioselectivity, which is attenuated by substitution of the α- and β-carbon atoms of the ketal.