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Synlett 2008(5): 683-686  
DOI: 10.1055/s-2008-1032107
LETTER
© Georg Thieme Verlag Stuttgart · New York

Enantioselective [1,2]-Stevens Rearrangement Using Sugar-Derived Alkoxides as Chiral Promoters

Katsuhiko Tomooka*a,b, Junichiro Sakamakib, Manabu Haradab, Ryoji Wadab
a Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga-shi, Fukuoka 8168580, Japan
Fax: +81(92)5837810; e-Mail: ktomooka@cm.kyushu-u.ac.jp;
b Department of Applied Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 1528552, Japan
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Publication History

Received 21 December 2007
Publication Date:
26 February 2008 (online)

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Abstract

The first example of enantioselective base-induced [1,2]-Stevens rearrangement was achieved by using the newly developed d-glucose-derived lithium alkoxide as a chiral promoter. This rearrangement provides an α-amino ketone having a pseudoquaternary chiral center in an enantioenriched form.

Key words

asymmetric synthesis - amines - carbohydrates - radical reactions - rearrangements

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7

All the ammonium salts were prepared from the corresponding α-amino ketones and alkyl bromides and purified by recrystallization.

8

Alkoxides were prepared from the corresponding alcohols using n-BuLi (1 equiv) at 0 °C.

14

HPLC analysis was carried out on a Chiralcel OD-H column (0.46 × 25 cm) using hexane-i-PrOH (150:1; 0.5 mL/min) as the mobile phase.

15

A rapid racemization of a similar chiral α-amino ketone under weakly basic conditions had been observed; see ref. 5e.

16

All the compounds were characterized by 1H and 13C NMR analyses. Data for selected products are as follows. 1b: 1H NMR (300 MHz, CDCl3): = 8.48 (d, J = 7.5 Hz, 2 H), 7.50-7.70 (m, 8 H), 6.88 (q, J = 7.2 Hz, 1 H), 5.29 (d, J = 12.0 Hz, 1 H), 5.06 (d, J = 12.0 Hz, 1 H), 3.42 (s, 3 H), 3.34 (s, 3 H), 1.79 (d, J = 7.2 Hz, 3 H). 13C NMR (75 MHz, CDCl3): = 196.8, 135.4, 134.0, 133.6, 131.0, 129.9, 129.5, 129.3, 126.7, 69.4, 66.5, 48.1, 47.0, 14.1. 2b: 1H NMR (300 MHz, CDCl3): = 8.46 (d, J = 6.9 Hz, 2 H), 6.90-7.50 (m, 8 H), 3.46 (d, J = 12.3 Hz, 1 H), 2.96 (d, J = 12.3 Hz, 1 H), 2.36 (s, 6 H), 1.18 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 203.1, 137.7, 137.6, 132.5, 130.9, 130.5, 128.3, 128.1, 126.5, 72.2, 41.2, 39.0, 14.5. 14: 1H NMR (300 MHz, acetone-d 6): = 5.83 (d, J = 3.6 Hz, 1 H), 4.48 (d, J = 3.6 Hz, 1 H), 4.38 (ddd, J = 6.6, 6.6, 8.4 Hz, 1 H), 4.16 (d, J = 2.7 Hz, 1 H), 4.12 (dd, J = 2.7, 6.6 Hz, 1 H), 4.10 (dd, J = 6.6, 8.1 Hz, 1 H), 3.80 (dd, J = 8.1, 8.4 Hz, 1 H), 2.82 (s, 1 H), 1.90-2.10 (m, 2 H), 1.40-1.60 (m, 10 H), 0.90 (s, 3 H), 0.90 (s, 3 H), 0.88 (s, 3 H), 0.87 (s, 3 H). 13C NMR (75 MHz, CDCl3): = 117.2, 112.7, 105.2, 84.6, 82.1, 75.6, 75.0, 71.2, 36.4, 35.6, 34.4, 33.7, 24.8, 23.8, 23.4, 17.4, 17.2.

17

Similar reactions using alkoxides 3-5 afforded racemic 2b in 16-29% yields.

23

Significant countercation-effect for enantioselectivity was observed, i.e., the reaction using the corresponding K or Na alkoxide of 8 afforded only the racemic 2b in moderate yields.

24

The enantioselectivity significantly decreased (18% ee), when one equivalent of 8 was used.

26

Typical Experimental Procedure: To a solution of 1,2-O-cyclohexylidene-5,6-O-(diisopropyl)methylidene-α-d-glucofuranose (14a; 104 mg, 0.29 mmol) in anhyd toluene (2 mL), was added a solution of n-BuLi (0.21 mL of 1.37 M solution in hexane, 0.29 mmol) at 0 °C. After stirring for 30 min at that temperature, benzyldimethyl(α-methylphen-acyl)ammonium bromide (1b; 10.0 mg, 0.029 mmol) was added. Then, the temperature of the resulting solution was allowed to rise to r.t. and the mixture was stirred for 8 h. The reaction was quenched with pH 7 phosphate buffer, and the product was extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, filtered, and the solvent was removed in vacuo. The residue was purified by silica gel chromatography to afford the α-amino ketone (S)-2b (7.0 mg, 91%, 61% ee) and recovered 14a (103 mg, 99%).