72128-69-9Relevant academic research and scientific papers
STEREOSELECTIVITY IN NUCLEOPHILIC ADDITION TO UNSATURATED LIGANDS BOUND TO MOLYBDENUM. ALLYLIC ALKYLATION OF CYCLOHEXANONE
Faller, J. W.,Lambert, C.
, p. 5755 - 5760 (1985)
The stereochemistry and regiochemistry of nucleophilic addition to olefinic, allylic, or diene moieties can be controlled in reactions of molybdenum complexes.The synthesis of a wide range of α-allylic cyclohexanones is feasible using (η5-cyclopentadienyl)Mo(CO)(NO)(allyl) cations.The stereoselective preparation of (RS,SR)-2-(1-methyl-2-butenyl)cyclohexanone from the reaction of 1-pyrrolidino-1-cyclohexene with (CpMo(CO)(NO)(η3-1,3-dimethylallyl))BF4 illustrates the methodology.
Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
supporting information, p. 1570 - 1573 (2014/04/17)
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
Dual palladium-and proline-catalyzed allylic alkylation of enolizable ketones and aldehydes with allylic alcohols
Usui, Ippei,Schmidt, Stefan,Breit, Bernhard
supporting information; experimental part, p. 1453 - 1456 (2009/09/30)
The dual Pd/proline-catalyzed α-allylation reaction of a variety of enolizable ketones and aldehydes with allylic alcohols is described. In this reaction, the choice of a large-bite angle ligand Xantphos and proline as the organocatalyst was essential for generation of the crucial π-allyl Pd intermediate from allylic alcohol, followed by nucleophilic attack of the enamine formed in situ from the corresponding enolizable carbonyl substrate and proline.
Polyethylene-Bound Soluble Recoverable Palladium(0) Catalysts
Bergbreiter, David E.,Weatherford, David A.
, p. 2726 - 2730 (2007/10/02)
The use of diphenylphosphine-terminated ethylene oligomers as ligands for palladium(0) and palladium(II) is described.With use of these polymeric ligands, it is possible to carry out homogeneous reactions characteristic of (Ph3P)4Pd and (Ph3P)2Pd(OAc)2 with essentially complete recovery of the Pd catalyst.The only limitation to repeated reuse of the catalyst is its immolative catalytic oxidation of the phosphine ligand by adventitious oxygen.
Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allylic Acetates with β-Keto Acids
Tsuda, Tetsuo,Okada, Masahiro,Nishi, Sei-ichi,Saegusa, Takeo
, p. 421 - 426 (2007/10/02)
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.
SYNTHESIS OF γ,δ-UNSATURATED KETONES BY THE INTRAMOLECULAR DECARBOXYLATIVE ALLYLATION OF ALLYL β-KETO CARBOXYLATES AND ALKENYL ALLYL CARBONATES CATALYZED BY MOLYBDENUM, NICKEL, AND RHODIUM COMPLEXES
Tsuji, Jiro,Minami, Ichiro,Shimizu, Isao
, p. 1721 - 1724 (2007/10/02)
Allyl β-keto carboxylates and alkenyl allyl carbonates were converted to γ,δ-unsaturated ketones by the intramolecular decarboxylative allylation catalyzed by molybdenum, nickel, and rhodium complexes.
