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43.3.3.1.3 Method 3: Rearrangement Reactions

DOI: 10.1055/sos-SD-043-00126

Gilchrist, T. L.Science of Synthesis, (200843215.

The most important method for the generation of para-arynes is Bergman cyclization. The prototypical reaction, that of (Z)-hex-3-ene-1,5-diyne (193), is illustrated in Scheme 82. The reaction was first described in detail in 1972,[‌291‌] but it has gained greater recognition and importance since 1987 following the discovery that several natural antibiotics contain the enediyne structural unit. The high activity of these compounds against a variety of cancers is related to their ability to abstract hydrogen atoms from the deoxyribose backbone of DNA, thereby causing cleavage of double-stranded DNA. It is generally assumed that Bergman cyclization precedes hydrogen abstraction in these antibiotics.

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References