Premium
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
Author(s) -
Melero Cristóbal,
Guijarro Albert,
Baumann Vitus,
PérezJiménez Ángel J.,
Yus Miguel
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200700447
Subject(s) - chemistry , reactivity (psychology) , naphthalene , biphenyl , norbornene , electrophile , aryl , propene , alkylation , intermolecular force , organic chemistry , medicinal chemistry , molecule , catalysis , alkyl , medicine , alternative medicine , monomer , pathology , polymer
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)