Continuous-Flow Kinetic Resolution of (±)-cis-1-Amino-2-indanol by Lipase-Catalyzed N-Acetylation

Abstract

Selective N-acetylation of (1S,2R)-1-amino-2-indanol by immobilized lipase B from Candida antarctica showed high enantiomeric excess when ethyl acetate was used as the acyl donor in a THF solution. Combining this process with continuous-flow system, we could obtain enantiomerically pure N-acetyl-aminoindanol at a flow rate of 0.1 mL/min (residence time of 64 min). It has been demonstrated to be more efficient compared to the flask mode.

Key words

(±)-cis-1-amino-2-indanol - Novozyme 435^® - continuous-flow system - kinetic resolution - selective N-acetylation

• References and Notes

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• 14 Flask Reaction – General Procedure To a separate small vials containing 0.2 M solutions of (±)-cis-1-amino-2-indanol (298 mg, 2.0 mmol) in THF–EtOAc (0.5 mL, 50 equiv), Novozyme 435^® (20 mg) was added to each vial in one portion, and the turbid solutions were shaken (125 rpm) at 30 °C. After 6 h, 12 h, 24 h, and 48 h, the enzyme was filtered off from the samples. For HPLC analysis, samples were diluted with EtOH (0.5 mL).
• 15 (1S,2R)-1-Acetamido-2-indanol (2) White solid; [α]_D ²⁰ +11.7 (c 0.25, CHCl₃). IR (neat): 3444, 3299, 1539 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.22 (s, 4 H), 6.23 (d, J = 7.2 Hz, NH), 5.32 (dd, J = 8.2, 5.1 Hz, 1 H), 4.57 (td, J = 5.1, 2.3 Hz, 1 H), 3.13 (dd, J =16.5, 5.3 Hz, 1 H), 291 (dd, J = 16.5, 2.1 Hz, 1 H), 2.57 (br s, 1 H), 2.07 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 170.9, 140.6, 139.9, 128.2, 127.2, 125.3, 124.5, 73.5, 57.6, 39.6, 23.3. ESI-HRMS: m/z calcd for C₁₁H₁₄NO₂ ⁺: 192.1019; found: 192.1016 [M + H]⁺.
• 16 Continuous-Flow Reaction, General Procedure Novozyme 435^® (2.0 g) was packed into a glass column with an aluminum heating jacket for maintaining temperature at 30 °C. The column was fully washed with THF and then fed with a solution of (±)-cis-1-amino-2-indanol (0.1 M) in EtOAc and THF (1:1). At various flow rates (2.0, 1.0, 0.5, 0.25, and 0.1 mL/min), 1 mL of samples were collected. For HPLC analysis, samples were diluted with EtOH (0.5 mL).