Reductive Bergman-Type Cyclizations of Cross-Conjugated Enediynes to Fulvene and Fulvalene Anions:  The Role of the Substituent

• Published in: Journal of the American Chemical Society 2006-04, Vol.128 (14), p.4703-4709
• Main Authors: Treitel, Noach, Eshdat, Lior, Sheradsky, Tuvia, Donovan, Patrick M, Tykwinski, Rik R, Scott, Lawrence T, Hopf, Henning, Rabinovitz, Mordecai
• Format: Article
• Language: English
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja0566477

Various cross-conjugated enediynes undergo “Bergman-type” cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at −78 °C. Not all cross-conjugated enediynes yield cyclized dianions upon reduction; some give uncyclized, Y-shaped, cross-conjugated dianions, while others apparently yield radical−anions that either dimerize or persist as monomers. One system yields both a cyclized and an uncyclized dianion. The substituents are thus shown to be a critical factor in determining the outcome of the reduction. Cyclization occurs within a specific “window of opportunity” that is governed by the substituents.