Carbolithiation of Simple Terminal and Strained Internal Alkenes by the Naphthalene and the Biphenyl Dianion: New Modes of Reactivity of Highly Reduced Organic Species in Solution

✍ Scribed by Cristóbal Melero; Albert Guijarro; Vitus Baumann; Ángel J. Pérez-Jiménez; Miguel Yus

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 373 KB
• Volume: 2007
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200700447

✦ Synopsis

Abstract

Dianions derived from arenes of high reduction potential (biphenyl, naphthalene) and Li~(s)~ can carbometallate propene, isobutene or norbornene among other alkenes, in an intermolecular fashion. This reaction runs at room temperature to afford partially dearomatized alkylated aryl anions that are susceptible to further functionalization by electrophilic capture. This form of reactivity, typical of the arene dianion, deviates from the specific alkali metal‐like reactivity displayed by these complexes, affording regio‐ and in many cases stereo‐controlled products. DFT calculations help to figure out the regiochemical outcome of this reaction, where some of the most inexpensive organic starting materials are involved. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)