Synthesis and Late-Stage Modification of (-)-Doliculide Derivatives Using Matteson's Homologation Approach.

(-)-Doliculide, a marine cyclodepsipeptide derived from the Japanese sea hare, Dolabella auricularia, exhibits potent cytotoxic properties, sparking interest in the field of synthetic chemistry. It is comprised of a peptide segment and a polyketide moiety, rendering it amenable to Matteson's homologation methodology. This technique facilitates the diversification of the distinctive polyketide side chain, thereby permitting the introduction of functional groups in late stages for modifications of the derived compounds and studies on structure-activity relationships.

Stereoselective Synthesis of Secondary and Tertiary Boronic Esters via Matteson Homologation.

Matteson homologations of chiral boronic esters with lithium dichlorocarbenoids and various nucleophiles proved to be a useful method for the synthesis of functionalized polyketides in a highly stereoselective fashion. Via repeated homologation steps, only 1,2-anti- and 1,3-syn-configured products were obtained. Homologation with substituted carbenoids followed by reaction with carbon nucleophiles resulted in configurationally inverted products and tertiary boronic esters in a highly stereoselective fashion. This approach significantly expands the potential of the Matteson reaction.

B and C domain containing tenascin-C: urinary markers for invasiveness of urothelial carcinoma of the urinary bladder?

PURPOSE: Surveillance of urothelial carcinoma of the urinary bladder (UBC) patients with respect to tumour recurrence and invasiveness is crucial for therapy and prognosis. Therefore, evaluation of non-invasive methods to monitor tumour progression is of high clinical interest. The study was aimed at investigating urinary concentrations of tenascin-C splicing domains for their value as tumour surveillance markers. METHODS: Urinary concentration of B and C domain containing tenascin-C (Tn-C) was analysed by ELISA technology in 104 UBC patients, 11 patients with cystitis and 15 healthy donors as control. The investigation was supplemented by Tn-C immunohistochemistry and Western blotting. RESULTS: A statistically significant increase in urinary concentrations of both Tn-C B and C domain with tumour progression could be evidenced. A concordant tumour-associated enhanced protein deposition in the carcinoma stroma could be demonstrated by immunohistochemistry in invasive UBC. Western blotting reveals proteolytic fragmentation of urinary Tn-C. CONCLUSIONS: In summary, detection of Tn-C splicing domains in urine is suggested as a marker for the surveillance of UBC recurrence and invasiveness.