Diverse modes of reactivity of 6-(chloromethyl)-6-methylfulvene.

The title compound exhibits a number of reactivities toward nucleophiles/bases owing to the presence of several electrophilic and potentially nucleophilic sites in the molecule. We explored the reactions of 6-(chloromethyl)-6-methylfulvene with oxygen- and nitrogen nucleophiles and bases as well as a carbon-based nucleophile (an enamine) and realized all possible reactivity modes predicted on the basis of electrophilic and nucleophilic positions in this compound.

Pyrrolidine catalyzed reactions of cyclopentadiene with α,ß-unsaturated carbonyl compounds: 1,2- versus 1,4-additions.

A systematic study of the reactions of cyclopentadiene with α,ß-unsaturated carbonyl compounds in the presence of catalytic pyrrolidine-H2O revealed that the reactions can either proceed with a Michael attack at the ß-carbon of enone, or 1,2-addition to the carbonyl, leadingeither to 4-cyclopentadienyl-2-butanones or 6-vinylfulvenes. The former can be isolated and/or converted to the corresponding 1,2-dihydropentalenes with base (or in one-pot at longer reaction times). Substitution pattern on the enones on the competing pathways have been studied and consistent mechanisms are proposed.

An efficient catalytic method for fulvene synthesis.

The effects of the nature and amount of base, substrate structure, amount of added water and solvent on the condensation of carbonyl compounds with cyclopentadiene in the presence of secondary amines were investigated. Based on these studies, a new efficient and green synthesis of fulvenes was developed.

Evidence for the existence of pyrimidinergic transmission in rat brain.

The uridine nucleotides uridine-5'-triphosphate (UTP) and uridine-5'-diphosphate (UDP) have previously been identified in media from cultured cells. However, no study to date has demonstrated their presence in brain extracellular fluid (ECF) obtained in vivo. Using a novel method, we now show that UTP and UDP, as well as uridine, are detectable in dialysates of striatal ECF obtained from freely-moving rats. Intraperitoneal (i.p.) administration of uridine or exposure of striatum to depolarizing concentrations of potassium chloride increases extracellular uridine, UTP and UDP, while tetrodotoxin (TTX) decreases their ECF levels. Uridine administration also enhances cholinergic neurotransmission which is accompanied by enhanced brain levels of diacylglycerol (DAG) and inositol trisphosphate (IP3) and blocked by suramin, but not by PPADS (pyridoxalphosphate-6-azophenyl-2',4'-disulfonic acid) or MRS2578 suggesting a possible mediation of P2Y2 receptors activated by UTP. These observations suggest that uridine, UTP and UDP may function as pyrimidinergic neurotransmitters, and that enhancement of such neurotransmission underlies pharmacologic effects of exogenous uridine on the brain.

1,2-Dihydropentalenes from fulvenes by [6 + 2] cycloadditions with 1-isopropenylpyrrolidine.

In situ generated acetone pyrrolidine enamine undergoes [6 + 2] cycloadditions with fulvenes to give 1,2-dihydropentalenes. This ring annulation method works particularly well with 6-monosubstituted fulvenes and is subject to steric hindrance at C-6 of the fulvene. On the basis of mechanistic studies, optimal conditions have been developed for a one-pot synthesis of 1,2-dihydropentalenes using catalytic amounts of pyrrolidine.