Investigation into the absolute stereochemistry of the marine sponge alkaloid pyrinodemin A

The absolute configuration of the marine sponge alkaloid pyrinodemin A is established by organic synthesis.     

Diastereoselective ring-closing metathesis: synthesis of P-stereogenic phosphinates from prochiral phosphinic acid derivatives

[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation into the factors influencing the diastereochemical outcome of the ring-closing metathesis is also presented, revealing that the geometry of the double bonds conjugated to phosphorus is important and that 1,3-stereoinduction is superior to 1,4-stereoinduction for these reactions.     

High-performance liquid chromatographic analysis of bile pigments as their native tetrapyrroles and as their dipyrrolic azosulfanilate derivatives

A reversed-phase high-performance liquid chromatographic (HPLC) analysis of bile pigments is described that provides baseline separation of the major bilirubin conjugates found in bile. The advantage of the technique is that the bile pigments can be analyzed directly as their native tetrapyrroles without prior solvent extractions or derivatization. The use of ammonium acetate in place of sodium salts permits preparative isolation and lyophilization of the pigments for mass spectroscopy. The derivatization of the pigments as their dipyrrolic azosulfanilates with subsequent HPLC analysis demonstrates baseline separation of the endo- and exovinyl azodipyrroles and allows identification of that half of the tetrapyrrole which contains the conjugate in the instances of monoglycosides.     

On complemented subspaces of (Σl_2 )_{l_p }

It is shown that ifX is a complemented subspace of (Σ (1<p<∞), thenX is isomorphic to eitherl ₂,l _p,l ₂⊗l _p or (Σ . IfX is a complemented subspace ofC _p(1<p<∞) which does not contain an isomorph of (Σ which does not contain an isomorph of thenX is isomorphic to a complemented subspace of (Σ ⊗l ₂. This research was partially supported by NSF MPS 72-04634-A03.     

An improved palladium(II)-catalyzed method for the synthesis of aryl ketones from aryl carboxylic acids and organonitriles

A palladium(II)-catalyzed decarboxylative protocol for the synthesis of aryl ketones has been developed. The addition of TFA was shown to improve the reaction yield and employing THF as solvent enabled the use of solid nitriles and in only a small excess. Using this method, five different benzoic acids reacted with a wide range of nitriles to produce 29 diverse (hetero)aryl ketone derivatives in up to 94% yield.