Chiral N,N′-Dioxide-Scandium(III)-Catalyzed Asymmetric Dearomatization of 2-Naphthols through an Amination Reaction

• Published in: Chemistry : a European journal Vol. 21; no. 48; pp. 17453 - 17458
• Main Authors: Lian, Xiangjin, Lin, Lili, Wang, Guojin, Liu, Xiaohua, Feng, Xiaoming
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 23.11.2015; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: amination reaction; asymmetric catalysis; Asymmetry; Carbon; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; dearomatization; naphthols; Optical activity; Physical Sciences; scandium; Science & Technology; HIGHLY ENANTIOSELECTIVE SYNTHESIS; OXIDATIVE DEAROMATIZATION; dearomatization; naphthols; EFFICIENT SYNTHESIS; scandium; ELECTROPHILIC AMINATION; ALDEHYDES; asymmetric catalysis; amination reaction; ALPHA-AMINATION; CONSTRUCTION; PHENOL DEAROMATIZATION; DERIVATIVES; CRAFTS ALLYLIC ALKYLATION
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201503276

A catalytic asymmetric dearomatization of 2‐naphthols with azodicarboxylates has been accomplished by using a N,N′‐dioxide‐scandium(III) complex as a chiral catalyst. A number of optically active β‐naphthalenone compounds with a nitrogen‐containing quaternary carbon stereocenter were obtained in up to 99 % yield and up to 99 % ee under mild reaction conditions. The reaction could be scaled up to a gram‐scale with the yield and ee maintained. Based on these experiments and on previous reports, a possible transition state was proposed. Animate you aminations! A catalytic asymmetric dearomatization of 2‐naphthols with azodicarboxylates has been accomplished by using a N,N′‐dioxide–scandium(III) complex as a chiral catalyst (see scheme). A number of optically active β‐naphthalenone compounds with a nitrogen‐containing quaternary carbon stereocenter were obtained under mild reaction conditions.