Synlett 2015; 26(20): 2817-2820
DOI: 10.1055/s-0035-1560538
cluster
© Georg Thieme Verlag Stuttgart · New York

Nickel-Catalyzed Enantioselective Friedel–Crafts Alkylation of Indoles with β,β-Disubstituted Nitroalkenes

Hao Wu
a  School of Chemical Engineering, Ningbo University of Technology, Cuibo Road 89#, Ningbo 315016, P. R. of China
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
,
Wei-Jian Sheng
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
,
Bin Chen
a  School of Chemical Engineering, Ningbo University of Technology, Cuibo Road 89#, Ningbo 315016, P. R. of China
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
,
Ren-Rong Liu
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
,
Jian-Rong Gao
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
,
Yi-Xia Jia*
b  College of Chemical Engineering, Zhejiang University of Technology, Chaowang Road 18#, Hangzhou 310014, P. R. of China   Email: yxjia@zjut.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 27 July 2015

Accepted after revision: 30 October 2015

Publication Date:
23 November 2015 (online)


Abstract

An enantioselective Friedel–Crafts alkylation of indoles with β,β-disubstituted nitroalkenes was developed by using a nickel(II) perchlorate–bisoxazoline complex as a catalyst. A range of nitroalkenes and indoles participated in this reaction, affording chiral indole compounds bearing all-carbon quaternary stereocenters in excellent yields and with moderate to good enantioselectivities (up to 80% ee).

Supporting Information

 
  • References and Notes


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  • 12 Indoles 3; General Procedure A dried Schlenk tube was charged with Ni(ClO4)2·6H2O (7.3 mg, 0.02 mmol) and ligand L5 (11.7 mg, 0.024 mmol) under N2. Toluene (2.0 mL) was then added from a syringe and the mixture was stirred at 50 °C for 1 h. The appropriate nitroalkene 2 (0.2 mmol) and indole 1 (0.3 mmol) were added, and the mixture was stirred at 50 °C until the reaction was complete (TLC). The solvent was removed under vacuum, and the residue was purified by chromatography [silica gel, EtOAc–PE (1:4)].
  • 13 3-[(1S)-1-Methyl-2-nitro-1-phenylethyl]-1H-indole (3aa) White solid; 90% yield, 77% ee; mp 145–146 °C; [α]D 20 +47.6 (c 0.5, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ = 2.03 (s, 3 H), 5.16 (d, J = 10.5 Hz, 1 H), 5.26 (d, J = 10.5 Hz, 1 H), 6.62–6.97 (m, 2 H), 7.15–7.18 (m, 2 H), 7.26–7.34 (m, 5 H), 7.38 (d, J = 8.0 Hz, 1 H), 8.11 (s, 1 H). 13C NMR (125 MHz, CDCl3): δ = 26.8, 43.8, 84.6, 111.5, 119.2, 119.5, 120.5, 122.2, 125.2, 126.5, 127.0, 128.5, 136.9, 143.9. HRMS (ESI+): m/z [M + Na]+ calcd for C18H15F3N2NaO2: 371.0983; found: 371.099. HPLC [Daicel Chiralpak AD-H column (25 × 0.46 cm), hexane–i-PrOH (90:10), 1.0 mL/min, λ = 254 nm]: tminor  = 18.5 min, tmajor  = 17.1 min.
  • 14 The absolute configuration of product 3aa was assigned as S; for details see the Supporting Information.