One-Pot Preparation of Chiral Dinuclear Vanadium(V) Complex

Abstract

A convenient one-pot procedure for the preparation of dinuclear vanadium(V) complex is described. The complex exhibited high catalytic activity for oxidative coupling of 2-naphthol derivatives. In addition, coupling of 9-phenanthrol gave (S)-10,10′-dihydroxy-9,9′-biphenanthryl in quantitative yield with 93% ee.

Key words

oxidative coupling - dinuclear vanadium complex - dual activation - biphenanthrol - asymmetric synthesis

References and Notes

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6

General Procedure for the One-Pot Preparation of (R _a , S , S)-1
A round-bottomed flask was charged with (R)-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl (2, 500 mg,
1.46 mmol), (S)-tert-leucine (3, 383 mg, 2.92 mmol), VOSO₄˙H₂O (952 mg, 5.84 mmol), MS 3 Å (1.46 g) and MeOH (50 mL) under O₂ (balloon). The reaction mixture was refluxed, and the consumption of 2 was monitored by TLC (acetone-hexane, 1:3). The resulting solution was gradually cooled down to r.t. and filtered through Celite to remove MS 3 Å. The filtrate was evaporated, and the resulting black solid was dissolved in CH₂Cl₂ and washed with H₂O. The organic phase was dried over anhyd Na₂SO₄ and concentrated in vacuum to give (R _a ,S,S)-1 (738 mg, 69%) as a black powder. Compound (R _a ,S,S)-1: ^¹H NMR (270 MHz, CD₃OD): δ = 8.96 (s, 2 H, CH=N), 8.48 (s, 2 H, ArH), 8.06 (t, J = 4.7 Hz, 2 H, ArH), 7.70 (t, J = 4.9 Hz, 2 H, ArH), 7.44-7.38 (m, 4 H, ArH), 4.23 (s, 2 H, CHt-Bu), 1.25 (s, 18 H, t-Bu). ^¹³C NMR (67.7 MHz, CD₃OD): δ = 167.9, 138.7, 137.6, 130.6, 130.5, 129.6, 127.4, 125.3, 124.1, 83.8, 38.8, 28.2. ^5¹V NMR (CD₃OD): δ = -557.2. IR: 3436 (OH), 1683 (C=N), 1608 (C=O), 996 (V=O) cm^-¹. HRMS-FAB: m/z calcd for C₃₄H₃₅N₂O₁₀V₂: 733.1171 [M + H]⁺; found: 733.1185.

7

The catalyst 1 prepared by the two-step promoted coupling reaction of 2-naphthol to afford (S)-BINOL with 96% yield and 85% ee in 24 h at r.t. under air.

11

Representative Procedure for the Oxidative Coupling of 9-Phenanthrol Using ( R _a , S , S )-1 In a round-bottomed flask (500 mL) was taken CH₂Cl₂ (240 mL) and 9-phenanthrol (5, 6.0 g, 30.9 mmol). Compound (R _a ,S,S)-1 (1.1 g, 1.54 mmol) was charged, and the reaction vessel was purged with O₂ (balloon). The reaction was stirred for 48 h at -10 ˚C. A short column to remove the catalyst gave (S)-4 in quantitative yield with 90% ee. Single recrystallization of the product thus obtained with hexane-acetone (5:4) gave optically pure (S)-4 in 79% yield.
Compound (S)-4: >99% ee, [α]_D ^²³ -65.7 (c 1.2, CHCl₃).