Kinetic Resolution of dl-Hydrobenzoins Catalyzed by Copper(II) Complexes of C2-Symmetric Thiophene-Derived Ligands

Woraluk Mansawat; Phanomsak Yukhet; Worawan Bhanthumnavin; Oliver Reiser; Tirayut Vilaivan

doi:10.1055/a-1815-7091

Synlett, Inhaltsverzeichnis

Synlett 2022; 33(14): 1405-1410
DOI: 10.1055/a-1815-7091

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Organic Chemistry in Thailand

Kinetic Resolution of dl-Hydrobenzoins Catalyzed by Copper(II) Complexes of C ₂-Symmetric Thiophene-Derived Ligands

Woraluk Mansawat

^aOrganic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

^bInstitute of Organic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany

,

Phanomsak Yukhet

^aOrganic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

,

Worawan Bhanthumnavin

^aOrganic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

,

Oliver Reiser ∗

^bInstitute of Organic Chemistry, University of Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany

,

Tirayut Vilaivan ∗

^aOrganic Synthesis Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Pathumwan, Bangkok 10330, Thailand

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Abstract

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Abstract

C ₂-Symmetrical chiral amino alcohol ligands with a central thiophene moiety were shown to be effective in combination with CuCl₂ for the asymmetric acylation of dl-hydrobenzoins. In contrast to previously developed chiral ligands, readily available acetyl chloride and acetic anhydride can be used as reagents, in addition to benzoyl chloride, giving rise to the corresponding monoacylated products in up to 99% ee (S = 532).

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References and Notes
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31 Ligands 1a–1l; General Procedure A mixture of the appropriate chiral amino alcohol (1.0 or 2.0 mmol) and aldehyde (1.0 mmol) in EtOH (5 mL) was refluxed for 4 h. The mixture was cooled to 0 °C and NaBH₄ (5.0 mmol) was added. When the amine had been consumed (TLC), the reaction was quenched with 10% aq HCl. The mixture was neutralized with sat. aq NaHCO₃, then concentrated under reduced pressure. The residue was extracted with EtOAc and washed with H₂O. The organic layer was dried (Na₂SO₄) and concentrated to give a crude product that was purified by flash column chromatography (silica gel, PE–EtOAc gradient). (2R,2'R)-2,2'-[Thiene-2,5-diylbis(methyleneimino)]bis(2-phenylethanol) (1g) Prepared according to the general method from thiophene-2,5-dicarbaldehyde (0.140 g, 1.0 mmol) and (R)-phenylglycinol (0.274 g, 2.0 mmol) as a white solid; yield: 0.325 g (85%); mp 103–105 °C; [α]_D ²⁵ = –58.4 (c 1.0, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.41–7.28 (m, 10 H), 6.66 (s, 2 H), 3.89 and 3.73 (AB, J = 14.0 Hz, 2 × 2 H), 3.85 (ABX, J _BX = 9.0, J _AX = 4.2 Hz, 2 H), 3.69 (ABX, J _AB = 10.9, J _AX = 4.3 Hz, 2 H), 3.57 (ABX, J _AB = 10.9, J _BX = 8.9 Hz, 2 H), 2.72 (br s, 4 H). ¹³C NMR (101 MHz, CDCl₃): δ = 142.8, 139.9, 128.8, 127.8, 127.4, 124.9, 66.7, 63.3, 45.9. HRMS (ESI⁺): m/z [M + H]⁺ calcd for C₂₂H₂₇N₂O₂S: 383.1793; found: 383.1809. Anal. Calcd for C₂₂H₂₆N₂O₂S: C, 69.08; H, 6.85; N, 7.32. Found: C, 69.16; H, 6.86; N, 7.38
32 Screening of Catalytic Activities: General Procedure The appropriate chiral ligand (0.025 mmol) and Cu(II) salt (0.025 mmol) were dissolved in CH₂Cl₂ (1.5 mL) and the mixture was stirred at rt for 2 h to afford a green homogeneous solution. The racemic 1,2-diol (0.25 mmol) and DIPEA (42.5 μL, 0.25 mmol) were added, and the mixture was cooled to 0 °C for 1 h. The appropriate acylating agent (0.125 mmol, 0.5 equiv) was added, and the mixture was stirred at 0 °C for 2 h then diluted with H₂O and extracted with CH₂Cl₂ (×3). The combined organic layers were dried (MgSO₄), concentrated under reduced pressure, and purified by chromatography (silica gel, PE–EtOAc). Enantioselectivities were determined by chiral HPLC (Chiralcel OJ-H^® column, heptane–i-PrOH). (1R,2R)-1,2-Bis(4-bromophenyl)-2-hydroxyethyl Acetate (5e) White solid; yield: 44% (99% ee). HPLC [OD-H column, heptane–i-PrOH (9:1), λ = 215 nm, flow rate: 0.5 mL/min]: T _R: 19.3 min (minor isomer); 23.9 min (major isomer). ¹H NMR (300 MHz, CDCl₃): δ = 7.42–7.33 (m, 4 H), 7.00–6.95 (m, 4 H), 5.72 (d, J = 7.5 Hz, 1 H), 4.85 (d, J = 7.5 Hz, 1 H), 2.62 (br s, 1 H), 2.12 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 170.0, 137.7, 135.5, 131.5, 131.4, 129.0, 128.7, 122.5, 122.3, 79.2, 76.2, 21.1. HRMS (EI-MS): m/z [M⁺] calcd for C₁₆H₁₄Br₂O₃: 411.9310; found: 411.9314

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Supporting Information

Kinetic Resolution of dl-Hydrobenzoins Catalyzed by Copper(II) Complexes of C 2-Symmetric Thiophene-Derived Ligands

Kinetic Resolution of dl-Hydrobenzoins Catalyzed by Copper(II) Complexes of C ₂-Symmetric Thiophene-Derived Ligands