Directed Metalation-Suzuki-Miyaura Cross-Coupling Strategies: Regioselective Synthesis of Hydroxylated 1-Methyl-phenanthrenes

作者：Jorgensen Kare B; Rantanen Toni; Doerfler Thilo; Snieckus Victor

来源：Journal of Organic Chemistry, 2015, 80(19): 9410-9424.

DOI：10.1021/acs.joc.5b01300

A general, efficient, and regioselective synthesis of a series of hydroxylated 1-methylphenanthrenes 9 by a combined directed ortho metalation (DoM)-Suzuki-Miyaura cross-coupling directed remote metalation (DreM) sequence is reported. Diversity to this methodology was achieved by a regioselective DoM rather than DreM reaction, affording more highly substituted phenanthrols (Table 2). Application of the turbo-Grignard reagent (i-PrMgCl-LiCl) in the Ni-catalyzed Corriu-Kumada reaction gave efficient decarbamoylation (Tables 3 and 4). Additional features are the TMS protecting group and halo-induced ipso-desilylation tactics applied to the regioselective synthesis of phenanthrenes (Scheme 2).

• 出版日期2015-10-2