(Hetero)aromatics from dienynes, enediynes and enyne–allenes

Target-directed enediynes: designed estramycins.

The goal of selective targeting of enediyne cytotoxins has been investigated using estrogenic delivery vehicles. A series of estrogen-enediyne conjugates were assembled, and affinity for human estrogen receptor [hERalpha] was determined. The most promising candidate induced receptor degradation following Bergman cycloaromatization and caused inhibition of estrogen-induced transcription in T47-D...

Antitumor antibiotics: bleomycin, enediynes, and mitomycin.

Reaction of arynes, N-heteroaromatics and nitriles.

Various N-heteroaromatic compounds, including pyridines, quinolines and isoquinoline, react with arynes and nitrile-containing solvents to give N-arylated 1,2-dihydro-2-pyridinyl, -2-quinolinyl and -1-isoquinolinyl nitriles in excellent yields.

Tetrahydroxy 10-membered cyclic enediynes.

The preparation of cyclic 10-membered tetrahydroxy enediynes is reported. The synthesis starts from tartaric acid and allows the control of the relative stereochemistry. Acetal protection of the 2,3-hydroxy groups stabilizes the enediyne during synthesis. Removal of the cyclic protecting group with EtSH/TFA transforms the stable compounds into reactive enediynes, and the rate constants of their...

Palladium-Catalyzed Oxidative Regio- and Diastereoselective Diarylating Carbocyclization of Dienynes

Transmetallation: A highly regio- and diastereoselective carbocyclization involving a palladium-catalyzed 1,2-addition of two carbon atoms across a conjugated diene has been developed (see scheme). The reaction is performed with dienynes and an oxygen tether containing a terminal or internal triple bond.