Isothiourea-Catalysed Sequential Kinetic Resolution of Acyclic (±)-1,2-Diols

Abstract

The isothiourea-catalysed acylative kinetic resolution of a range of acyclic (±)-1,2-diols using 1 mol% of catalyst under operationally simple conditions is reported. Significantly, the bifunctional nature of (±)-1,2-diols was exploited in a sequential double kinetic resolution, in which both kinetic resolutions operate synergistically to provide access to highly enantioenriched products. The principles that underpin this process are discussed, and selectivity factors for the individual kinetic resolution steps are reported in a model system.

Key words

kinetic resolution - isothiourea - 1,2-diols - enantioselectivity - acylation

• References and Notes

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• 19 (±)-1,2-Diphenylethane-1,2-diol (2)THF (4 equiv.) was added to a solution of TiCl₄ (1 equiv.) in anhydrous CH₂Cl₂ (0.5 M) under an N₂ atmosphere at r.t. and was allowed to stir for 30 s. Zinc powder (0.5 equiv.) was added, and after a further 30 s N,N,N′,N′-tetramethylethylenediamine (1.5 equiv.) was added. After 30 s, a solution of benzaldehyde (1 mL, 10 mmol, 1 equiv.) in CH₂Cl₂ (1 M) was added and the mixture allowed to stir at r.t. for 1 h. HCl (1 M) was added and the mixture extracted with EtOAc (3 times). The combined organic fractions were washed with brine, dried (Na₂SO₄), filtered and concentrated to give a residue, which was purified by Biotage flash silica column chromatography (0→40% EtOAc in n-hexane) to give a colourless solid, which was further purified by recrystallisation: the material was dissolved hot PhMe/hexane (1:1), allowed to cool to r.t. and then cooled in a freezer overnight. The product was filtered and washed with cold hexane to give (±)-1,2-diphenylethane-1,2-diol as colourless crystals (single diastereoisomer, 768 mg, 3.59 mmol, 72% yield). Mp 121 °C (Lit.²⁵ mp 121 °C); ¹H NMR (500 MHz, CDCl₃): δ = 2.84 (s, 2 H, OH), 4.72 (s, 2 H, HCOH), 7.10–7.16 (m, 4 H, ArH), 7.21–7.27 (m, 6 H, ArH). Spectral data in accordance with the literature.²⁸
• 20 KR of (±)-1,2-Diols: General ProcedureHyperBTM 1 (x mol%), (i-PrCO)₂O (y equiv.) and i-Pr₂NEt (z equiv.) were added to a solution of the appropriate (±)-1,2-diol (1 equiv.) in the given solvent (0.2 M) and at the given temperature, and the mixture allowed to stir for 7 h. HCl (1 M) was added and the mixture extracted with EtOAc (3 times). The combined organic fractions were washed sequentially with saturated NaHCO₃ and brine, dried (Na₂SO₄), filtered and concentrated to give a residue, which was purified by Biotage flash silica column chromatography (0→40% EtOAc in hexane) to give the diester, monoester and diol products, which were analysed by HPLC using a chiral support – see Supporting Information for more details.
• 21 This s value was calculated by usings = ln[(1−c)(1−ee_substrate)] / ln[(1−c)(1+ee_substrate)]and assumes the reaction is irreversible and the er of the diol substrate is exclusively determined by the selectivity associated with the first KR process.
• 22 See Supporting Information for more details.
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• 24 In contrast, the selectivity factor (s) of a single step KR is, by definition, independent of conversion. See references 7a and 7b.
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• 26 Both enantiomers are available from Apollo Scientific {(2S,3R) CAS Reg. No. [1203507-02-1]; (2R,3S) CAS Reg. No. [1699751-03-5]}.
• 27 The research data underpinning this publication can be found at: https://doi.org/10.17630/45a265c9-c200-47ef-979d-cb3ed157e4c0.
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