Iridium-Catalyzed Decarboxylative N-Alkylation of α-Amino Acids with Primary Alcohols

Jiashou Wu; Huajiang Jiang; Dingben Chen; Jianfen Shen; Datong Zhao; Jing Xiang; Qizhong Zhou

doi:10.1055/s-0033-1340474

Synlett, Table of Contents

Synlett 2014; 25(4): 539-542
DOI: 10.1055/s-0033-1340474

letter

Iridium-Catalyzed Decarboxylative N-Alkylation of α-Amino Acids with Primary Alcohols

Authors

Jiashou Wu*

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)85137169 Email: jsw79@tzc.edu.cn

^bZhejiang Hisoar Pharmaceutical Co., LTD., Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)88828200 Email: zhaodt@hisoar.com
Huajiang Jiang

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)85137169 Email: jsw79@tzc.edu.cn
Dingben Chen

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)85137169 Email: jsw79@tzc.edu.cn
Jianfen Shen

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)85137169 Email: jsw79@tzc.edu.cn
Datong Zhao*

^bZhejiang Hisoar Pharmaceutical Co., LTD., Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)88828200 Email: zhaodt@hisoar.com
Jing Xiang

^cCollege of Chemistry and Environmental Engineering, Yangtze University, Jingzhou 434020, Hubei, P. R. of China
Qizhong Zhou

^aSchool of Pharmaceutical and Chemical Engineering, Taizhou University, Taizhou 318000, Zhejiang, P. R. of China Fax: +86(576)85137169 Email: jsw79@tzc.edu.cn

Abstract

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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.

Key words

iridium - amine - decarboxylative N-alkylation - amino acid - alcohol

Full Text

References

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.