A group of homologous 2,4-diketones with chain lengths from C13 to C25, derived from fatty acids, is present in human and mammalian tissues and urine. The presence of this lipid class, members of which possess marked chelating properties, adequately accounts for the well-documented antiallergic activity of tissue and urine extracts on isolated smooth muscle preparations and in guinea pigs in vi...

Monovalent group 13 diyls are versatile reagents in oxidative addition reactions. We report here [1,4]-cycloaddition reactions of β-diketiminate-substituted LM (M = Al, Ga, In, Tl; L HC[C(Me)NDipp]2, Dipp 2,6-iPr2C6H3) with various 1,2-diketones to give 5-metalla-spiro[4.5]heterodecenes 1, 4–6, and 8–10, respectively. In contrast, the reaction LTl acenaphthenequinone gave [2,3]-cycloaddition pr...

Two approaches to the synthesis of 2-chloro-9-(2-deoxy-2-fluoro-β-D-arabinofuranosyl)adenine (1, clofarabine) were studied. The first approach consists in the chemical synthesis of 2-deoxy-2-fluoro-α-D-arabinofuranose-1-phosphate (12a, (2F)Ara-1P) via three step conversion of 1,3,5-tri-O-benzoyl-2-deoxy-2-fluoro-α-D-arabinofuranose (9) into the phosphate 12a without isolation of intermediary pr...

Herein we describe the enantioselective intermolecular conjugate addition of nitroalkanes to unactivated α,β-unsaturated esters, catalyzed by a bifunctional iminophosphorane (BIMP) superbase. The transformation provides most direct access pharmaceutically relevant enantioenriched γ-nitroesters, utilizing feedstock chemicals, with unprecedented selectivity. methodology exhibits broad substrate s...

An electron-withdrawing group was introduced to the α-position of chalcones, and the resulting alkylidene diketones showed new reactivities with enals under the catalysis of N-heterocyclic carbenes (NHCs). Selective activation of enals affords enolate equivalents that undergo highly enantioselective intermolecular Diels-Alder reactions with the alkylidene diketones. No products that might have ...

We report herein a point-to-axial chirality transfer reaction of optical dihydrophenanthrene-9,10-diols for the synthesis axially chiral diketones. Two sets conditions, namely basic tBuOK/air atmosphere and an acidic NaClO/n-Bu4NHSO4, were developed to oxidatively cleave C-C bond, resulting in formation biaryl Finally, brief synthetic applications obtained aryl diketones demonstrated.