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Synlett 2014; 25(2): 270-274
DOI: 10.1055/s-0033-1340251
DOI: 10.1055/s-0033-1340251
letter
Enzyme and Gold Catalysis: A New Enantioselective Entry into Functionalized 4-Hydroxy-2-pyrrolines
Weitere Informationen
Publikationsverlauf
Received: 24. September 2013
Accepted: 14. Oktober 2013
Publikationsdatum:
13. November 2013 (online)
![](https://www.thieme-connect.de/media/synlett/201402/lookinside/thumbnails/10.1055-s-0033-1340251-1.jpg)
Abstract
A new route toward functionalized pyrrolines starting from acetylenic aldehydes was developed. Key steps involved a hydroxynitrile lyase catalyzed asymmetric hydrocyanation of acetylenic aldehydes and a gold-catalyzed cyclization of substituted acetylene-containing amino alcohols.
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References and Notes
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- 16 Representative Procedures (R)-2-[(tert-Butyldimethylsilyl)oxy]-4-phenylbut-3-ynenitrile (9) A solution of 3-phenyl-2-propynal (8, 2.42 g, 15.4 mmol) in MTBE (15 mL) was added to a cooled (0 °C) solution of KCN (10.0 g, 154 mmol, 10.0 equiv) in citrate buffer (15 mL, pH 5.0). After addition of a lysate of (R)-HNL17 (4 mL) the reaction mixture was stirred at 0 °C for 4 h and quenched with 5 M HCl (10 mL). The precipitated enzyme was filtered over a glass funnel filled with cotton. The filtrate was extracted with CH2Cl2 (3 × 50 mL), and the organic layers were combined, dried (Na2SO4), and concentrated in vacuo. The residue was dissolved in dry CH2Cl2 (150 mL) at 0 °C, and TBSCl (2.79 g, 1.2 equiv) and imidazole (2.10 g, 2.0 equiv) were added. After stirring overnight at r.t., the mixture was quenched with sat. aq NH4Cl the aqueous layer was extracted with CH2Cl2 (3 × 40 mL). The organic layers were combined, dried (Na2SO4), and concentrated in vacuo. Purification by column chromatography (EtOAc–heptane, 0:1 to 1.5:8.5) afforded 9 (3.60 g, 86% yield) as a yellow oil. Rf = 0.69 (EtOAc–heptane, 1:3). [α]D 20 –7.2 (c 1.33, CH2Cl2); 95% ee [Chiralpak AD-H column: HPLC eluent hexane–i-PrOH (85:15), flow 1.0 mL/min]; t R1 = 6.12 min (S); t R1 = 7.01 min (R). IR (ATR): 2958, 2928, 2855, 2228, 2202, 1489, 1256, 1091, 836, 780, 759, 694 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.49–7.46 (m, 2 H), 7.42–7.33 (m, 3 H), 5.50 (s, 1 H), 0.95 (s, 9 H), 0.28 (s, 3 H), 0.26 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 132.0, 129.7, 128.6, 121.0, 116.5, 87.1, 81.9, 52.7, 25.6, 18.3, –4.6. HRMS (EI): m/z calcd for C16H21NOSi: 271.1392; found: 271.1394. (1S,2R)-2-[(tert-Butyldimethylsilyl)oxy]-1,4-diphenyl-but-3-yn-1-amine (22) To a solution of 9 (1.00 g, 3.68 mmol) in dry Et2O (37 mL) was added dropwise PhMgBr (3.68 mL of a 3.0 M solution in Et2O, 3.0 equiv) at 0 °C. After 5 min the reaction mixture was stirred at r.t. for 2 h. Then dry MeOH (15 mL) was added, and the reaction mixture was cooled to –78 °C followed by dropwise addition of a solution of freshly prepared Zn(BH4)2 in THF–Et2O (1:1) in 30 min, and the reaction mixture was stirred overnight. The mixture was quenched with sat. aq NaHCO3 (20 mL) and the product extracted with EtOAc (3 × 20 mL). The organic layers were combined, dried (Na2SO4) and concentrated in vacuo. Purification by column chromatography (EtOAc–heptane, 0:1 to 3:7) afforded 22 (742 mg, 58% yield) as a yellow oil [inseparable mixture of diastereoisomers (1:8)]. Major diastereoisomer: Rf = 0.34 (EtOAc–heptane, 1:3). [α]D 20 –12.4 (c 1.71, CH2Cl2). IR (ATR): 3031, 2957, 2922, 2850, 1666, 1593, 1493, 1359, 1251, 1091, 836, 788, 758, 702 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.44–7.27 (m, 10 H), 4.61 (d, J = 5.9 Hz, 1 H), 4.10 (d, J = 5.9 Hz, 1 H), 1.99 (br s, 2 H), 0.85 (s, 9 H), 0.04 (s, 3 H), –0.01 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 141.5 131.7, 128.5, 128.4, 128.2, 127.7, 127.6, 122.9, 88.6, 86.4, 69.9, 61.5, 29.9, 25.9, –4.6, –5.1. ESI-HRMS: m/z calcd for C22H30NOSi [M + H]+: 352.2097; found: 352.2086. (4R,5S)-N-tert-Butoxycarbonyl-2,5-diphenyl-4-hydroxy-2-pyrroline (38) To a solution of 30 (50.0 mg, 0.11 mmol) in dry THF (2 mL) was added dropwise TBAF (110 μL, 1.1 equiv) at 0 °C. The reaction mixture was warmed to r.t. and stirred for 1 h. It was quenched with sat. aq NH4Cl (10 mL), diluted with CH2Cl2 (10 mL), and extracted with CH2Cl2 (3 × 10 mL). The organic layers were combined, dried (Na2SO4), and concentrated in vacuo. The resulting colorless oil was dissolved in dry THF (2 mL) and NaAuCl4·2H2O (4.4 mg, 0.1 equiv) was added at r.t. The reaction temperature was increased to 50 °C, and the mixture was stirred for 6 h. After cooling to r.t., Et3N (10 μL, 5.0 equiv) was added, and the solvent was removed in vacuo. Purification by column chromatography [EtOAc–heptane–1% Et3N (v/v), 0:1 to 1:3] afforded 38 (30 mg, 87% yield) as a yellowish oil. Rf = 0.17 [EtOAc–heptane–1% Et3N (v/v), 1:3]. [α]D 20 +22.4 (c 0.71, CH2Cl2). IR (ATR): 3408, 2980, 2924, 1698, 1636, 1367, 1166, 1018, 752, 697 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.52–7.48 (m, 2 H), 7.42–7.36 (m, 7 H), 7.32–7.26 (m, 1 H), 5.34 (dd, J = 0.4, 3.3 Hz, 1 H), 5.10 (d, J = 1.2 Hz, 1 H), 4.35 (dd, J = 1.2, 3.3 Hz, 1 H), 1.15 (s, 9 H). 13C NMR (75 MHz, CDCl3): δ = 154.4, 149.6, 142.5, 135.3, 129.8, 129.5, 128.9, 128.5, 126.3, 112.2, 82.1, 79.5, 74.2, 60.2, 28.1. ESI-HRMS: m/z calcd for C21H24NO3 [M + H]+: 338.1756; found: 338.1769.
- 17 The gene encoding for (S)-HNL, originating from the rubber tree Hevea brasiliensis, was cloned and efficiently expressed in the yeast strain Pichia pastoris as an intracellular protein; the enzyme preparation was obtained by homogenization (French press) of the cells, removal of insolubles by filtration, and subsequent concentration of the clear filtrate using ultrafiltration/diafiltration.18 The wild-type gene encoding for (R)-HNL, originating from bitter almonds (Prunus amygdalus), was cloned and efficiently expressed in the yeast strain Pichia pastoris. The enzyme was secreted from the cells and was obtained from cell-free supernatant by concentration using ultrafiltration/diafiltration.19 The crude lysates (cell-free extracts) containing (R)-HNL and (S)-HNL were kindly provided by DSM Innovative Synthesis (Geleen, the Netherlands).
- 18 Hasslacher M, Schall M, Hayn M, Bona R, Rumbold K, Luckl J, Griengl H, Kohlwin SD, Schwab H. Protein Expression Purif. 1997; 11: 61
- 19 Glieder A, Weis R, Skranc W, Poechlauer P, Dreveny I, Majer S, Wubbolts M, Schwab H, Gruber K. Angew. Chem. Int. Ed. 2003; 42: 4815
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