Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives.
Angew Chem Int Ed Engl. 2016 Mar 01; 55(10):3496-9.AC

Abstract

An iridium-catalyzed intramolecular asymmetric allylic dearomatization reaction of naphthol derivatives is described. Challenges confronted in this reaction include chemoselectivity between carbon and oxygen atoms as nucleophilic centers, diastereoselectivity when contiguous chiral centers are generated, and enantioselective control for constructing an all-carbon quaternary stereocenter. In the presence of an iridium catalyst generated from [{Ir(dbcot)Cl}2] (dbcot=dibenzocyclooctatetraene) and a new THQphos (tetrahydroquinolinedinaphthophosphoramidite) ligand, various spironaphthalenones were obtained with up to greater than 95:5 C/O selectivity, greater than 95:5 d.r., and 99 % ee, thus providing a general method for the dearomatization of naphthols.

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Authors+Show Affiliations

Cheng Q

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.

Wang Y

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.

You SL

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China. slyou@sioc.ac.cn.

Pub Type(s)

Journal Article

Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

26848021

Citation

Cheng, Qiang, et al. "Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives." Angewandte Chemie (International Ed. in English), vol. 55, no. 10, 2016, pp. 3496-9.

Cheng Q, Wang Y, You SL. Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives. Angew Chem Int Ed Engl. 2016;55(10):3496-9.

Cheng, Q., Wang, Y., & You, S. L. (2016). Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives. Angewandte Chemie (International Ed. in English), 55(10), 3496-9. https://doi.org/10.1002/anie.201511519

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives. AU - Cheng,Qiang, AU - Wang,Ye, AU - You,Shu-Li, Y1 - 2016/02/05/ PY - 2015/12/11/received PY - 2016/2/6/entrez PY - 2016/2/6/pubmed PY - 2016/2/6/medline KW - aromaticity KW - asymmetric catalysis KW - iridium KW - ligand effects KW - spiro compounds SP - 3496 EP - 9 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 55 IS - 10 N2 - An iridium-catalyzed intramolecular asymmetric allylic dearomatization reaction of naphthol derivatives is described. Challenges confronted in this reaction include chemoselectivity between carbon and oxygen atoms as nucleophilic centers, diastereoselectivity when contiguous chiral centers are generated, and enantioselective control for constructing an all-carbon quaternary stereocenter. In the presence of an iridium catalyst generated from [{Ir(dbcot)Cl}2] (dbcot=dibenzocyclooctatetraene) and a new THQphos (tetrahydroquinolinedinaphthophosphoramidite) ligand, various spironaphthalenones were obtained with up to greater than 95:5 C/O selectivity, greater than 95:5 d.r., and 99 % ee, thus providing a general method for the dearomatization of naphthols. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/26848021/Chemo__Diastereo__and_Enantioselective_Iridium_Catalyzed_Allylic_Intramolecular_Dearomatization_Reaction_of_Naphthol_Derivatives_ DB - PRIME DP - Unbound Medicine ER -

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Chemo-, Diastereo-, and Enantioselective Iridium-Catalyzed Allylic Intramolecular Dearomatization Reaction of Naphthol Derivatives.Angew Chem Int Ed Engl. 2016 Mar 01; 55(10):3496-9.AC