Boron trifluoride-catalyzed reaction of alkyl fluoride with silyl enolate, allylsilane, and hydrosilane
Alkylation of silyl enolates with tert-alkyl or allylic fluorides proceeds smoothly in the presence of a catalytic amount of boron trifluoride to afford the corresponding carbonyl compounds. Allylation and reduction of alkyl fluorides with allylsilane and hydrosilane, respectively, occur under BF 3 catalysis.
Stereoselective Synthesis of (E)- and (Z)-γ,δ-Unsaturated Ketones Using trans-2-Phenylthiocyclobutyl Ketones
The reaction of 1-methoxymethyl-2-phenylthiocyclobutanes with phenylthiotrimethylsilane followed by hydrolysis gave (E)- and (Z)-γ,δ-unsaturated ketones with high stereoselectivity.The starting materials were easily prepared by the stereoselective addition of Grignard reagents to trans-2-phenylthiocyclobutyl ketones.
Fujiwara, Tooru,Iwasaki, Toshiaki,Takeda, Takeshi
p. 1321 - 1324
(2007/10/02)
Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allylic Acetates with β-Keto Acids
In the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium, β-keto acids react with allylic acetates at ambient temperature to produce α-allylic ketones in good yields with quantitative decarboxylation.This palladium-catalyzed decarboxylative allylic alkylation of allylic acetates with β-keto acids is characterized by high regio- and stereoselectivity.Allylation of β-keto acid takes place at the carbon atom bearing a carboxyl group.Allylic alkylation of allylic acetate with β-keto acid occurs at the less substituted end of the allyl group.The resultant carbon-carbon double bond of the α-allylic ketone has the E configuration.Allylic alkylation of lactone 25 with benzoylacetic acid proceeds preferably with retention of configuration, indicative of trans attack of the enolate on the (?-allyl)palladium intermediate from the opposite side of palladium even in the coexistence of free carboxylic acids.
A one-pot procedure for the reductive alkylation of β-keto sulfones is described.The method proceeds by a lithium in liquid ammonia desulfurization of the starting β-keto sulfone, resulting in regiospecific generation of an intermediate enolate.Subsequent
Kurth, Mark, J.,O'Brien, Michael, J.
p. 3846 - 3848
(2007/10/02)
Countercation Effects on the Palladium-Catalyzed Allylation of Enolates
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Negishi, Ei-ichi,John, Robert A.
p. 4098 - 4102
(2007/10/02)
Highly Regio- and Stereospecific Palladium-Catalyzed Allylation of Enolates Derived from Ketones
The reaction of potassium enoxyborates, readily obtainable by treating potassium enolates with a trialkylborane, e.g., triethylborane, with allylic electrophiles such as allylic chlorides and acetates in the presence of a catalytic amount of a palladium-p
Negishi, Ei-ichi,Matsushita, Hajime,Chatterjee, Sugata,John, Robert A.
p. 3188 - 3190
(2007/10/02)
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