Bifunctional Thiourea Catalyzed Asymmetric Mannich Reaction Using Trifluoromethyl Aldimine as Trifluoromethyl Building Blocks

Shilong Ji; Ahmed Ebrahim Alkhalil; Yingpeng Su; Xiaowen Xia; Siying Chong; Ke-Hu Wang; Danfeng Huang; Ying Fu; Yulai Hu

doi:10.1055/s-0034-1380693

Synlett, Table of Contents

Synlett 2015; 26(12): 1725-1731
DOI: 10.1055/s-0034-1380693

letter

Bifunctional Thiourea Catalyzed Asymmetric Mannich Reaction Using Trifluoromethyl Aldimine as Trifluoromethyl Building Blocks

Shilong Ji

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Ahmed Ebrahim Alkhalil

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Yingpeng Su*

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Xiaowen Xia

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Siying Chong

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Ke-Hu Wang

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Danfeng Huang

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Ying Fu

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

,

Yulai Hu*

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, 967 Anning Road (E.), Lanzhou, Gansu 730070, P. R. of China Email: huyl@nwnu.edu.cn Email: suyp51@nwnu.edu.cn

^bState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China

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Abstract

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Abstract

An efficient bifunctional thiourea catalyzed asymmetric Mannich reaction with trifluoromethyl aldimine as trifluoromethyl building block was achieved to give the products in good diastereoselectivity and enantioselectivity.

Key words

thiourea catalysts - trifluoromethyl aldimine - β-keto esters - Mannich reaction - bifunctional organocatalyst

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References

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21 General Procedure for Preparing 4To the mixture of 2 (0.158 mmol, 1 equiv) and 3 (0.189 mmol, 1.2 equiv) in i-Pr₂O (2 mL), DIPEA (0.237 mmol, 1.5 equiv) and thiourea catalyst 1g (9.4 mg, 10 mol%) were added successively into a flame-dried flask at 10 °C under Ar atmosphere. The mixture was stirred at 10 °C for 72 h. When the reaction was completed, the mixture was concentrated under reduced pressure. The residue was purified by flash column chromatography using PE–EtOAc–CH₂Cl₂ (7:1:1) as eluent to obtain the desired product 4.Data of Compound 4a Yield 80%; white solid; mp 148–150 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.80–7.78 (d, J = 7.6 Hz, 1 H), 7.68–7.64 (t, J = 7.6 Hz, 1 H), 7.55–7.53 (d, J = 8.0 Hz, 1 H), 7.43–7.39 (t, J = 7.6 Hz, 1 H), 6.81 (s, 4 H), 5.23–5.15 (m, 1 H), 4.07–4.03 (d, J = 17.2 Hz, 1 H), 3.76 (s, 3 H), 3.71–3.68 (d, J = 11.6 Hz, 1 H), 3.56 (s, 3 H), 3.43–3.39 (d, J = 17.2 Hz, 1 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 196.7, 167.5, 153.7, 152.3, 139.4, 135.8, 133.9, 129.4–120.9 (q, J _C–F = 284.3 Hz), 128.0, 126.4, 125.1, 116.1, 114.7, 63.9, 60.9–60.1 (q, J _C–F = 27.8 Hz), 55.5, 53.3, 31.4 ppm. ¹⁹F NMR (376 MHz, CDCl₃): δ = –70.36 to –70.38 (d, J = 6.8 Hz) ppm. ESI-HRMS: m/z calcd for C₂₀H₁₈F₃NO₄ [M + H]⁺: 394.1261; found: 394.1258. IR (thin film): 3370, 3032, 2961, 1745, 1514, 1465, 1245, 1033, 828, 760 cm^–1. HPLC: major ee = 84%; minor ee = 88%; dr = 80:20 [Chiralpak AD-H, n-hexane–i-PrOH (90:10), 1 mL/min, 254 nm]: t ₁ (major isomer) = 17.70 min, t ₂ (major isomer) = 29.28 min; t ₃ (minor isomer) = 11.97 min, t ₄ (minor isomer) = 22.82 min.

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22b Nakano J, Masuda K, Yamashita Y, Kobayashi S. Angew. Chem. Int. Ed. 2012; 51: 9525

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