Asymmetric Henry Reactions of Aldehydes Using Chiral Biaryl-Based Bis(thiourea) Organocatalysts

Yuki Nakayama; Yusaku Hidaka; Katsuji Ito

doi:10.1055/s-0032-1318490

Synlett, Table of Contents

Synlett 2013; 24(7): 883-885
DOI: 10.1055/s-0032-1318490

letter

Asymmetric Henry Reactions of Aldehydes Using Chiral Biaryl-Based Bis(thiourea) Organocatalysts

Yuki Nakayama

,

Yusaku Hidaka

,

Katsuji Ito*

Abstract

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Abstract

Biaryl-based bis(thiourea) was found to be an efficient organocatalyst for the asymmetric Henry reaction. High enantioselectivity of up to 93% ee was obtained for the reaction of nitromethane with aryl aldehydes when the combination of N,O-bis(trimethylsilyl)trifluoroacetoamide (BSTFA) with a catalytic amount of potassium acetate was used as the base.

Key words

asymmetric catalysis - bis(thiourea) - Henry reaction - nucleophilic addition - enantioselectivity

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References

References and Notes
1 Present address: Institute for Materials Chemistry and Engineering (IMCE), Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan.

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16 Use of the combination of BSTFA and KOAc as a base for palladium-catalyzed asymmetric allylic substitution: Ito K, Kashiwagi R, Hayashi S, Uchida T, Katsuki T. Synlett 2001; 284
17 Typical Experimental Procedure is Exemplified by Henry Reaction of 4-Nitrobenzaldehyde with Nitromethane Catalyst 1 (8.1 mg, 10.0 μmol) was placed in microtube under nitrogen and to this tube was added BSTFA (5.5 μL, 20.0 μmol) in DMF (100 μL), a catalytic amount of KOAc (0.4–0.5 mg, 4.1–5.1 μmol), and 4-nitrobenzaldehyde (16.1 mg, 0.1 mmol). After the mixture was cooled to –40 °C, MeNO₂ (55 μL, 1.0 mmol) was added at that temperature. After being stirred for 23 h at –40 °C, the mixture was quenched with H₂O and extracted with EtOAc. The organic extract was dried over anhyd MgSO₄ and concentrated. Silica gel chromatography of the residue (hexane–Et₂O = 6:4) gave the desired product (19.3 mg, 91%). The ee of the product was determined to be 91% by HPLC using chiral stationary-phase column as described in the footnote of Table 1.
18 Time-course studies suggested that the retro process is not involved in the reaction (3 h: 15% yield, 89% ee, 6 h: 35% yield, 88% ee, 12 h: 47% yield, 88% ee, 24 h: 90% yield, 89% ee). For the retro process in the asymmetric Henry reaction using organocatalyst, see ref. 7b.
19 We also examined the reaction of aldehydes and EtNO₂, but the reaction did not proceed.
20 Absolute configuration of all nitro alcohols were determined by comparison of elution order of HPLC and specific rotation with the reported value.^4b,g,j,9

21a At the moment, we have no evidence that the nitronate anion is generated under the optimized conditions. However, we believe that the nitronate anion from MeNO₂ (pK _a = 10.2) is generated, because the imidate anion generated from BSA or BSTFA and KOAc can deprotonate dimethyl malonate (pK _a = 13).
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