TY - JOUR AU - Panossian, Armen AU - Leroux, Frédéric R. PY - 2016/02/24 Y2 - 2024/03/29 TI - Lithium/Element Exchange as an Efficient Tool for Accessing Atropo-enriched Biaryls via Arynes JF - CHIMIA JA - Chimia VL - 70 IS - 1-2 SE - Scientific Articles DO - 10.2533/chimia.2016.43 UR - https://www.chimia.ch/chimia/article/view/2016_043 SP - 43 AB - This account documents the development of transition metal-free, aryne-mediated aryl-aryl coupling, the 'ARYNE coupling', which began in 2001 in Lausanne. ortho,ortho'-Di-, tri- and even tetrasubstituted biphenyls have now become accessible on a multi-gram scale. The reaction is perfectly regioselective and the obtained polybromobiphenyls can be submitted to regioselective bromine/lithium interconversions. The access to enantiopure biphenyls is now possible using enantiopure sulfoxides as chiral auxiliaries, which allow for subsequent chemoselective sulfoxide/metal exchange on each atropo-diastereoisomer with configurational stability of the intermediate biaryllithiums. Direct atropo-diastereoselective ARYNE coupling has been reported more recently. ER -