A new efficient method for the generation of F-alkyl ketone metal enolates by using copper(II) bromide-lithium aluminium hydride reagent and their aldol reaction with carbonyl compounds

Kuroboshi, Manabu; Okada, Yoshiji; Ishihara, Takashi; Ando, Teiichi

doi:10.1016/s0040-4039(00)96337-8

Cited by 21 publications

(1 citation statement)

References 18 publications

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“…Reaction of these fluorinated enol phosphates with a reagent prepared from lithium aluminum hydride (LiAIH 4 ) and copper(II) bromide, zinc(II) chloride, tin(II) chloride or bromine afforded the enolate (Scheme 34). 124 The reaction of the enol phosphate with the reagents mentioned above suggests that the metal cation of the enolate is an aluminum species, though its actual structure is not known at present.…”

Section: Aluminum Enolatesmentioning

confidence: 99%

2.06 Formation of Enolates

Mekelburger

Wilcox

2014

Comprehensive Organic Synthesis II

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Section: Aluminum Enolatesmentioning

confidence: 99%

2.06 Formation of Enolates

Mekelburger

Wilcox

2014

Comprehensive Organic Synthesis II

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Insertion, Reduction, and Carbon–Carbon Coupling Induced by Monomeric Aluminum Hydride Compounds Bearing Substituted Pyrrolyl Ligands

Lin¹,

Tsai²,

Chen³

et al. 2006

Chemistry A European J

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A monomeric aluminum hydride complex bearing substituted pyrrolyl ligands, AlH[C(4)H(3)N(CH(2)NMe(2))-2](2) (1), was synthesized and structurally characterized. To further confirm the presence of Al--H bonds, the compound AlD[C(4)H(3)N(CH(2)NMe(2))-2](2) ([D]1) was synthesized by reacting LiAlD(4) with [C(4)H(4)N(CH(2)NMe(2))-2]. Compound 1 and [D]1 react with phenyl isothiocyanate yielding Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCHNPh] (2) and Al[C(4)H(3)N(CH(2)NMe(2))-2](2)[eta(3)-SCDNPh] ([D]2) by insertion. The reactions of 1 with 9-fluorenone and benzophenone generated the unusual aluminum alkoxide complexes 3 and 4, respectively, through intramolecular proton abstraction and C-C coupling. A mechanistic study shows that 9-fluorenone coordinates to [D]1 and releases one equivalent of HD followed by C-C coupling and hydride transfer to yield the final product. Reduction of benzil with 1 affords aluminum enediolate complex 5 in moderate yield. Mechanistic studies also showed that the benzil was inserted into the aluminum hydride bond of [D]1 through hydroalumination followed by proton transfer to generate the final product [D]5. All new complexes have been characterized by (1)H and (13)C NMR spectroscopy and X-ray crystallography.

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