Asymmetric Mukaiyama Aldol Reaction Catalyzed by C ₂-Symmetric N,N′-Dioxide-Ni(II) Complex

Abstract

The N,N′-dioxide-Ni(II) complex has been developed for the asymmetric Mukaiyama aldol reaction between glyoxal derivatives and enolsilane which produced the 2-hydroxy-1,4-dicarbonyl compounds in moderate to high yields (up to 95%) with excellent enantioselectivities (up to 95% ee). Based on the configuration of the product and X-ray structure of the catalyst, a possible transition state was proposed to explain the mechanism of the reaction.

asymmetric catalysis - N,N′-dioxides complex - nickel - Mukaiyama aldol reaction - glyoxal derivatives

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General Procedure for the Asymmetric Mukaiyama Aldol Reaction between Glyoxal Derivative 1a and Enolsilane 3a:
Ligand L7 (0.01 mmol) and Ni(BF₄)₂˙6H₂O (0.01 mmol) were dissolved in CH₂Cl₂ (0.5 mL) and stirred at 30 ˚C for 1 h. Then the solvent was removed and glyoxal derivative 1a (0.1 mmol) was added. After adding CH₂Cl₂ (1.0 mL) and enolsilane 3a (0.15 mmol), the mixture was stirred at 30 ˚C for 24 h under N₂ atmosphere. Then, THF (2.0 mL) and 1 N HCl (1.0 mL) were added to the reaction mixture. After stirring at r.t. for 30 min, this solution was poured into a separatory funnel and diluted with Et₂O (5.0 mL) and H₂O (1.0 mL). After mixing, the aqueous layer was discarded and the ether layer was washed with sat. aq NaHCO₃ (5.0 mL) and brine (5.0 mL). The resulting ether layer was dried over anhyd MgSO₄, and concentrated in vacuo. The crude product was chromatographed on silica gel to give the desired adduct 5a: 94% yield; 92% ee {determined by HPLC analysis with a Chiral OJ-H column, hexane-2-PrOH (80:20), 1.0 mL/min, UV = 254 nm; t _R1 = 18.6 min, t _R2 = 20.5 min); [α]_D ^²5 +11.9 (c 0.454, in CH₂Cl₂}; ^¹H NMR (400 MHz, CDCl₃): δ = 3.37-3.49 (m, 2 H), 4.04 (d, J = 6.0 Hz, 1 H), 5.68-5.73 (m, 1 H), 7.46-7.55 (m, 4 H), 7.58-7.66 (m, 2 H), 7.95-8.01 (m, 4 H) ppm.