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Synlett 2010(5): 765-768  
DOI: 10.1055/s-0029-1219390
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Asymmetric Aza-Friedel-Crafts Reaction of 2-Naphthol with Tosylimines Catalyzed by a Dinuclear Zinc Complex

Liang-Feng Niu, Yang-Chun Xin, Ren-Lin Wang, Fan Jiang, Peng-Fei Xu, Xin-Ping Hui*
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P. R. of China
Fax: +86(931)8915557; e-Mail: xphui2003@yahoo.com.cn; e-Mail: huixp@lzu.edu.cn;
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Publication History

Received 20 October 2009
Publication Date:
10 February 2010 (online)

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Abstract

The first asymmetric aza-Friedel-Crafts reaction of 2-naphthol with tosylimines was developed via a dinuclear zinc catalyst (up to 98% ee). It provided a new method for the asymmetric synthesis of Betti base derivatives.

Key words

2-naphthol - asymmetric synthesis - Betti base - Friedel-Crafts reaction - tosylimine

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13

The preparative procedure of the dinuclear zinc complex, see Supporting Information for full details.

14

General Procedure for Aza-Friedel-Crafts Reaction
To a solution of ligand 2 (r.t., 192 mg, 0.3 mmol) in toluene (4 mL) in a Schlenk tube was added dropwisely a solution of diethylzinc (0.68 mL, 0.6 mmol) under a nitrogen atmo-sphere. The solution was continued to stir for 1 h to give a solution of complex 2 (0.75 M in toluene). 2-Naphthol (43 mg, 0.3 mmol) and tosylimine (0.9 mmol) were added, and the reaction was stirred for 48 h at 30 ˚C. After the reaction was completed, the mixture was quenched with sat. NH4Cl solution (5 mL) and EtOAc (5 mL). The organic layer was separated, and the aqueous phase was extracted with EtOAc (3 × 5 mL). The combined organic layers were dried over Na2SO4. The solvent was removed under reduced pressure using a rotary evaporator. The residue was purified by column chromatography using CH2Cl2-PE-EtOAc = 10:10:1 to give the desired product.
N -[(2-Hydroxynaphthalen-1-yl)(phenyl)methyl]-4-methylbenzenesulfonamide (4a) Yield 90%; light yellow solid; [α]D ²0 -55 (c 1.0, CHCl3); mp 142-144 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 7.2 Hz, 1 H), 7.70 (d, J = 4.4 Hz, 1 H), 7.65-7.50 (m, 1 H), 7.40-7.37 (m, 1 H), 7.33-7.30 (m, 5 H), 7.25-7.20 (m, 3 H), 6.87-6.83 (m, 1 H), 6.64 (d, J = 8.0 Hz, 3 H), 6.48 (s, 1 H), 6.39 (d, J = 8.4 Hz, 1 H), 2.09 (s, 3 H). ¹³C NMR (75 MHz, CDCl3): δ = 151.1, 142.8, 139.9, 135.9, 132.3, 129.6, 128.8, 128.7, 128.3, 127.2, 127.1, 126.7, 126.5, 123.3, 121.8, 118.1, 117.3, 54.4, 21.1. ESI-HRMS: m/z calcd for C24H21NO3S + Na: 426.1140; found: 426.1134. HPLC: ee 96% [Chiralcel OD-H, n-hexane-i-PrOH (95:5), flow rate: 1.0 mL/min]: t R(minor) = 20.36 min; t R(major) = 25.71 min.

15

The ee of compounds 4a-l were determined by HPLC using Chiralcel column, see Supporting Information for full details.

16

The molecular structure of product 4k was determined
by X-ray crystallography. CCDC 751078 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallo-graphic data centre via www.ccdc.cam.ac.uk/data_request/cif or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: +44 (1223)336033.

17

The preparative procedure of compound (S)-4a, see Supporting Information for full details.

18

Synthesis of Compound ( R )-5a
To dry degassed THF (2.5 mL) taken in a round-bottomed flask under nitrogen was added Na metal (69 mg, 3 mmol) following naphthalene (40 mg, 2.9 mmol). The mixture was stirred for 1 h at r.t. To this solution was added a concen-trated solution of (R)-4a (58 mg, 0.14 mmol) in dry THF (3 mL). The reaction was stirred at r.t. overnight. The mixture was quenched by addition of a small amount of H2O care-fully, the solution dried over anhydrous MgSO4 and filtered. The crude mass was purified by column chromatography to give (R)-5a (21.6 mg, 62%). ¹H NMR (300 MHz, CDCl3):
δ = 7.74-7.69 (m, 3 H), 7.49-7.35 (m, 2 H), 7.37-7.15 (m, 6 H), 6.16 (s. 1 H). HPLC: ee 94% [Chiralcel OJ, n-hexane-
i-PrOH (70:30), flow rate: 1.0 mL/min]: t R(minor) = 22.35 min; t R(major) = 51.87 min.