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Synlett 2014; 25(4): 539-542
DOI: 10.1055/s-0033-1340474
DOI: 10.1055/s-0033-1340474
letter
Iridium-Catalyzed Decarboxylative N-Alkylation of α-Amino Acids with Primary Alcohols
Weitere Informationen
Publikationsverlauf
Received: 27. September 2013
Accepted after revision: 24. November 2013
Publikationsdatum:
08. Januar 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201404/lookinside/thumbnails/10.1055-s-0033-1340474-1.jpg)
Abstract
A new decarboxylative N-alkylation reaction of α-amino acids has been developed. A variety of tertiary amines were obtained in good to excellent yields via the decarboxylative N-alkylation reaction of α-amino acids with primary alcohols catalyzed by a Cp*Ir complex.
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References and Notes
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- 6 General Procedure for the Preparation of 3 To a solution of [Cp*IrCl2]2 (0.0025 mmol), amino acid 2 (0.65 mmol), and NaHCO3 (0.05 mmol) in toluene (3 mL) under an atmosphere of argon was added alcohol 1 (0.5 mmol). The resulting mixture was stirred at 110 °C for a certain period of time. The reaction mixture was cooled to r.t., and H2O (5 mL) was then added. The resulting solution was extracted with EtOAc. Purification on silicon gel afforded the desired products 3. General Procedure for the Preparation of 4 To a solution of [Cp*IrCl2]2 (0.0075 mmol), glycine (2c, 0.5 mmol), and KOH (0.15 mmol) in toluene (3 mL) under an atmosphere of argon was added alcohol 1 (1.0 mmol). The resulting mixture was stirred at 110 °C for a certain period of time. The reaction mixture was cooled to r.t., and H2O (5 mL) was then added. The resulting solution was extracted with EtOAc. Purification on silicon gel afforded the desired products 4. Data of Unknown Compounds Compound 3n: yellow oil. IR: 3063, 3032, 2961, 2784, 1606, 1589, 1510, 1455, 1378, 1265, 1227, 1163, 1136, 1023, 853, 809, 736 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.49–7.40 (m, 4 H), 7.39–7.32 (m, 4 H), 7.32–7.27 (m, 2 H), 7.00 (d, J = 1.8 Hz, 1 H), 6.87 (d, J = 8.1 Hz, 1 H), 6.82 (dd, J = 8.2, 1.9 Hz, 1 H), 5.17 (s, 2 H), 5.14 (s, 2 H), 3.58 (s, 2 H), 2.58–2.46 (m, 4 H), 1.84–1.72 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 148.7, 148.3, 137.4, 137.3, 131.3, 128.5, 128.4, 127.8, 127.7, 127.4, 127.3, 122.2, 116.2, 114.8, 71.4, 71.2, 59.7, 53.6, 23.3 ppm. ESI-HRMS: m/z calcd for C25H27NO2 [M + H]: 374.2115; found: 374.2117. Compound 3o: yellow oil. IR: 3064, 3034, 2961, 2789, 1602, 1588, 1495, 1453, 1376, 1348, 1241, 1123, 1050, 1024, 880, 858, 754, 697 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.46–7.42 (m, 3 H), 7.41–7.37 (m, 2 H), 7.36–7.31 (m, 1 H), 7.24 (dt, J = 8.2, 2.1 Hz, 1 H), 6.93–6.99 (m, 2 H), 5.09 (s, 2 H), 3.91 (s, 2 H), 2.74–2.78 (m, 4 H), 1.85–1.80 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.8, 137.1, 131.5, 128.9, 128.6, 127.9, 127.3, 125.1, 120.9, 111.9, 53.2, 52.5, 23.3 ppm. ESI-HRMS: m/z calcd for C18H21NO [M + H]: 268.1696; found: 268.1695.
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