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Synlett 2014; 25(13): 1879-1882
DOI: 10.1055/s-0034-1378323
DOI: 10.1055/s-0034-1378323
letter
Lewis Base Catalyzed Asymmetric Hydrosilylation of α-Substituted β-Enamino Esters: Facile Access to Enantioenriched β2-Amino Esters via Dynamic Kinetic Resolution
Weitere Informationen
Publikationsverlauf
Received: 13. April 2014
Accepted after revision: 19. Mai 2014
Publikationsdatum:
08. Juli 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201413/lookinside/thumbnails/10.1055-s-0034-1378323-1.jpg)
Abstract
A chiral Lewis base organocatalyzed asymmetric hydrosilylation of α-substituted β-enamino esters is presented. The reactions proceeded through dynamic kinetic resolution to afford various enantioenriched β2-amino esters with high yields (up to 98%) in moderate enantioselectivities (up to 77% ee).
Key words
asymmetric catalysis - dynamic kinetic resolution - β2-amino acids - hydrosilylation - Lewis baseSupporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
- Supporting Information
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- 13 General Experimental Procedure for the Enantioselective Hydrosilylation of α-Substituted β-Enamino Esters A solution of trichlorosilane (41 μL, 0.3 mmol, 2.0 equiv) in 160 μL of CH2Cl2 was added to a stirred solution of the corresponding α-substituted β-enamino ester (0.20 mmol) and the catalyst 3i (0.020 mmol) in CH2Cl2 (2.0 mL) at –10 °C. The mixture was stirred at the same temperature until the reaction reached completion. Then the reaction was quenched with a sat. aq solution of NaHCO3 and was extracted with CH2Cl2. The combined organic layer was washed with brine, dried over anhydrous Na2SO4, and the solvents were evaporated. Purification by column chromatography (silica gel; hexane–EtOAc, 10:1) afforded the products. The ee values were determined using established HPLC techniques with chiral stationary phases.
- 14 Ethyl 2-(3,4-Dimethoxyphenyl)-3-(4-methoxyphenyl-amino)propanoate (2e) Yield 99%; 77% ee; light yellow oil. 1H NMR (300 MHz, CDCl3): δ = 6.76–6.84 (m, 5 H), 6.58 (d, J = 8.8 Hz, 2 H), 4.10–4.19 (m, 2 H), 3.86 (s, 6 H), 3.79–3.83 (m, 1 H), 3.72–3.74 (m, 4 H), 3.59 (br s, 1 H), 1.18–1.28 (m, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 173.0, 152.3, 149.1, 148.4, 141.4, 129.2, 120.3, 114.9, 114.6, 114.3, 110.9, 60.9, 55.8, 55.7, 50.3, 47.9, 14.0 ppm. ESI-HRMS: m/z calcd for [C20H25NO5 + H]+: 360.1811; found: 330.1804. [α]D 20 +112 (c 0.50, CHCl3). AD-H column (n-hexane–2-PrOH, 80:20), flow rate = 1.0 mL/min, t R = 16.7, 17.9 min.
For reviews, see:
For selected examples, see:
For reviews on Lewis base catalysis and Lewis base catalytic asymmetric hydrosilylations of C=N double bonds, see:
For representative examples, see:
For reviews on DKR, see:
For recent selected examples, see: