Preparation of Optically Active 1,2-Diol Monotosylates by Enzymatic Hydrolysis

Abstract

An easy preparation of optically active 1,2-diol monotosylate derivatives by enzymatic hydrolysis is disclosed. Lipase PS (Burkholderia cepacia) catalyzes the hydrolysis of racemic 2-acetoxyhexyl tosylate with excellent enantioselectivity to afford the corresponding optically active compounds. In this reaction, a unique temperature effect is observed. After optimizing the reaction conditions, this procedure is widely applicable to the practical preparation of both enantiomers of various optically active compounds with high ee.

Key words

enantioselective hydrolyses - enzymes - kinetic resolution - solvent effects - tosylates

References and Notes

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  For enzymatic hydrolysis in organic solvent, see ref. 5c. For enzymatic alcoholysis in organic solvent, see ref. 4g and 5a.

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7

The substrate (±)-1 was prepared form 1-hexene in 3 steps; 1) OsO₄, NMO, acetone-H₂O; 2) TsCl, Bu₂SnO, Et₃N, CH₂Cl₂; [18] 3) Ac₂O, pyridine. The details will be reported separately.

8

In the screening test, we used the following enzymes: lipase type II, type VII (Sigma), lipase PS, lipase AY, lipase A, PLE-A, lipase d-360, lipase AK, lipase D (Amano Enzyme, Inc.), lipase OF (Meito Sangyo Co., Ltd), lipase (Nagase ChemteX Corp.), Novozym (NovoNordisk A/S). The hydrolysis of (±)-1 with lipase type II, lipase type VII, PLE-A or lipase OF proceeded with low enantioselectivity. The other enzymes did not catalyze the reaction.

9

The absolute configurations of 1 and 2 were confirmed by comparing the obtained optical rotation value with the reported value: (R)-1, lit. [5a] [α]_D ²⁵ +13.4 (CHCl₃), 86% ee; (S)-2, lit. [5a] [α]_D ²⁵ +4.2 (CHCl₃), 66% ee.

10

The ee of 1 was determined by HPLC analysis with CHIRALCEL AD-H (Daicel Chemical Industries, Ltd.); eluent: hexane-i-PrOH (90:10); flow rate: 0.5 mL min^-1; t _R = 18 (S) and 19.5 (R) min. A similar analysis of 2 was also performed with CHIRALCEL OD-H; eluent: hexane-i-PrOH (95:5); flow rate: 0.5 mL min^-1; t _R = 32 (R) and 35.5 (S) min.

12

Compound (S)-1: ¹H NMR (300 MHz, CDCl₃): δ = 0.86 (t, J = 7.0 Hz, 3 H) 1.13-1.34 (m, 4 H), 1.46-1.65 (m, 2 H), 1.98 (s, 3 H), 2.46 (s, 3 H), 4.05 (dd, J ₁ = 5.5 Hz, J ₂ = 10.5 Hz, 1 H), 4.10 (dd, J ₁ = 3.5 Hz, J ₂ = 10.5 Hz, 1 H), 4.90-5.00 (m, 1 H), 7.35 (d, J = 8.5 Hz, 2 H), 7.79 (d, J = 8.5 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 13.7, 20.8, 22.2, 27.0, 30.0, 70.0, 70.9, 127.8, 130.0, 132.7, 145.0, 170.3. IR (neat): 3460, 2957, 2870, 1730, 1597, 1454, 1362, 1177 cm^-1. MS (EI): m/z (%) = 314 (7.2) [M⁺], 254 (27), 228 (38), 198 (16), 172 (16), 143 (36), 129 (17), 91 (100), 82 (16). HRMS: m/z [M⁺] calcd for C₁₅H₂₂O₅S: 314.1188; found: 314.1187.

13

Compound (R)-2: ¹H NMR (300 MHz, CDCl₃): δ = 0.87 (t, J = 7.0 Hz, 3 H), 1.10-1.53 (m, 6 H), 2.19 (br s, 1 H), 2.45 (s, 3 H), 3.78-3.91 (m, 1 H), 3.84-3.94 (m, 1 H), 4.00-4.08 (m, 1 H), 7.36 (d, J = 8.5 Hz, 2 H), 7.80 (d, J = 8.5 Hz, 2 H). ¹³C NMR (75 MHz, CDCl₃): δ = 13.8, 21.5, 22.4, 27.2, 32.2, 69.2, 73.9, 132.5, 144.9. IR (neat): 3539, 2955, 2872, 1599, 1454, 1360, 1177, 1098, 974 cm^-1. MS (EI): m/z (%) = 242 (25), 172 (11), 155 (52), 139 (10) 107 (20), 91 (100), 87 (42). HRMS: m/z [M⁺] calcd for C₁₃H₂₀O₄S: 272.1082; found: 272.1085.

16

In the cases of 3a and 3e, the isolated yields of the compounds were low for the high volatility.