Angew. Chem. Int. Ed. 2011, 50, 4455 –4458.pdfVIP

DOI: 10.1002/anie.201100206 Asymmetric Dearomatization Iridium-Catalyzed Intramolecular Asymmetric Allylic Dearomatization of Phenols** Qing-Feng Wu, Wen-Bo Liu, Chun-Xiang Zhuo, Zi-Qiang Rong, Ke-Yin Ye, and Shu-Li You* Dearomatization reactions provide the most direct synthesis nucleophiles in the iridium-catalyzed intramolecular allylic of ring systems starting from readily available aromatic dearomatization reactions (Scheme 1). This protocol would compounds.[1] The combination of a dearomatization reaction provide a direct access to enantiopure spirocyclohexadie- with asymmetric synthesis would lead to the enantioselective nones, which serve as a popular structural core in numerous construction of carbocyclic and heterocyclic derivatives.[2] biologically interesting natural products and pharmaceuticals. Despite progress in this area, the reported methods have so far focused on a stepwise protocol, which involves the dearomatization process and a subsequent asymmetric reac- Table 1: Optimization of the reaction conditions.[a] tion.[3] The direct asymmetric dearomatization reaction where the dearomatization and asymmetric catalysis occur in one step is highly desirable but very challenging.[4] As part of our recent studies on iridium-catalyzed allylic substitution reactions,[5–7] we found that iridium-catalyzed intramolecular asymmetric allylic alkylation of indole pro- vided enantioenriched spiroindolenine compounds.[8] Phenols are cheap and abundant chemicals widely used in organic synthesis. Transition-metal-catalyzed allylic alkyla- tion reactions of phenols generally proceeds as O allylation[9] with limited