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Gilchrist, T. L., Science of Synthesis, (2008) 43, 215.
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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Me eeeeeeeee eeeeee ee eeeeeeeeeee eee eeeeeeeeeee ee eeeee eee Meeeeee eeeeeeeeeee eeeee eeeee ee eee eeeeeeee e eeeeeee eee eeeeeeee eeeeee eeeee ee eee eeeeeeeee (Meeeee 88). Me eee eeeee ee eeeeeeeeeeee eeeeeeeeeeee eee eeeeeeeeeeee, ee ee eeeeeeeee eeee eeeeeeeee ee eeeee eee eeeeeeee eeeeeeee eeee ee eee eeeee 888–888 ee eeeeee eeeeeee eeeeeeeeeeeee ee eeee eeeeeeeeeee.[888,888,888] Mee eeeeee eeeeeeeee 888 (e = 8) eee 888 (e = 8) eeee eeeeeeee eeee eeeeeeeeeee ee 888 eee 888 ee, eeeeeeeeeeee, eee eee eeeeee ee eeee eeeeeeeeeee eeeeeee eee eeeeeeee 888 (e = 8), ee eeeee eee eeeeeeee ee 888 ee, ee eee (Meeeee 88).[888] Meee eeee eeee eee eeee eee eeeeeeeeeee eeeeee, eeeeeee. Mee eeeeeeeeeee 888 (M8 = Me; M8 = M), eeeee ee eeeeeeeee ee eeee eeeee eee eeee eeeeeeeeeee eeeeeeee ee 888 (M8 = M8 = M), eee e eeee eeee ee 8 eeeee ee 88°M, eee eee eeeeeeee eeeeeeee 888 (M8 = M8 = Me) eee e eeee eeee ee 88 eeeee ee 888°M.[888] Meeeeeee σ-eeeeeeee eee π-eeeee eeeeeeeeeeee eee eeeeeeeee ee eeeeeeeeeee eee eeeeeeee eeeeeeee ee eee eeee-eeeee, ee eee eeeeee eeee eee eeeeeeeeeee ee eee eeeeeeeeeeeeeeeeeee 888 ee eeeeeeeee ee ee eeeeeeeeee.[888] Mee eeeee eeeeee ee eee eeeeeeeee ee eeee eeeeeeeeeeee ee eee Meeeeee eeeeeeeeeee eeeeeee ee ee eeeeeeeeeee.
Meeeee 88 Meeeeeeeeee ee Meeeee Meeeeeeee[888]
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References
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