One-Pot Regioselective Synthesis of 2,5,6,7-Tetrahydroimidazo [1,2-a]imidazol-3-ones Starting from (Vinylimino)phosphoranes

Fen Tan; Zheng-Zheng Meng; Xiao-Qin Xiong; Guo-Ping Zeng; Ming-Wu Ding

doi:10.1055/s-0037-1611760

Synlett, Table of Contents

Synlett 2019; 30(07): 857-859
DOI: 10.1055/s-0037-1611760

letter

One-Pot Regioselective Synthesis of 2,5,6,7-Tetrahydroimidazo [1,2-a]imidazol-3-ones Starting from (Vinylimino)phosphoranes

Fen Tan

^aHubei Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients, Hubei University of Education, Wuhan 430205, P. R. of China Email: huashengxi2@163.com

,

Zheng-Zheng Meng

^aHubei Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients, Hubei University of Education, Wuhan 430205, P. R. of China Email: huashengxi2@163.com

,

Xiao-Qin Xiong

^aHubei Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients, Hubei University of Education, Wuhan 430205, P. R. of China Email: huashengxi2@163.com

,

Guo-Ping Zeng*

^aHubei Key Laboratory of Purification and Application of Plant Anti-cancer Active Ingredients, Hubei University of Education, Wuhan 430205, P. R. of China Email: huashengxi2@163.com

,

Ming-Wu Ding *

^bKey Laboratory of Pesticide and Chemical Biology of Ministry of Education, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Central China Normal University, Wuhan 430079, P. R. of China Email: mwding@mail.ccnu.edu.cn

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Abstract

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Abstract

A new, one-pot, regioselective preparation of 2,5,6,7-tetrahydroimidazo[1,2-a]imidazol-3-ones by a sequential aza-Wittig/nucleophilic addition/cyclization reaction was developed. The aza-Wittig reactions of ethyl (2Z)-3-aryl-2-[(triphenylphosphoranylidene)amino] acrylates with aryl isocyanates produced carbodiimide intermediates that were then treated sequentially with 2-aminoethanol and tosyl chloride/triethylamine to give the corresponding (2Z)-2-[(substituted)benzylidene]-2,5,6,7-tetrahydro-3H-imidazo[1,2-a]imidazol-3-ones in good overall yields and with high regioselectivity.

Key words

imidazoimidazolone - aza-Wittig reaction - nucleophilic addition - regioselectivity

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References

References and Notes

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21 CCDC 1862199 contains the supplementary crystallographic data for compound 6ab. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
22 (2Z)-2-Benzylidene-7-(4-tolyl)-2,5,6,7-tetrahydro-3H-imidazo[1,2-a]imidazol-3-one (6ab); Typical Procedure (Vinylimino)phosphorane 1a (2.26 g, 5 mmol) was treated with 4-tolyl isocyanate (2b; 0.67 g, 5 mmol) in CH₂Cl₂ (15 mL) at r.t. for 4 h to give carbodiimide 3ab (monitored by TLC), which was used directly in the next step. Ph₃P=O was extracted from the mixture with 1:2 Et₂O–PE (20 mL), and carbodiimide 3ab was treated with 2-aminoethanol (4; 0.60 mL, 5 mmol) in CH₂Cl₂ (15 mL) with stirring for 4 h. The mixture was then concentrated and the residue was dissolved in MeCN (25 mL). Et₃N (2.8 mL, 20 mmol) was added, followed after 30 min by TosCl (1.05 g, 5.5 mmol). The mixture was then stirred at r.t. for about 6 h until 5ab was completely consumed (TLC). The reaction was quenched with sat. aq NH₄Cl, and the mixture was extracted with CH₂Cl₂. The extracts were dried (Na₂SO₄) and the crude mixture was purified directly by flash column chromatography [silica gel PE–CH₂Cl₂ (4:1 to 2:1)] to give a light-yellow solid; yield: 1.24 g (82%); mp 196–198 °C.IR: 2954, 2924, 2854, 1730, 1659, 1603, 1591, 1565, 1519, 1492, 1459, 1376, 1305 cm^–1. ¹H NMR (600 MHz, CDCl₃): δ = 8.09 (d, J = 7.6 Hz, 2 H), 7.64 (d, J = 8.4 Hz, 2 H), 7.41 (t, J = 7.6 Hz, 2 H), 7.31 (t, J = 7.3 Hz, 1 H), 7.27–7.23 (m, 2 H), 6.76 (s, 1 H), 4.40–4.31 (m, 2 H), 4.00–3.90 (m, 2 H), 2.36 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 166.3, 158.7, 145.2, 135.9, 135.0, 133.2, 130.9, 129.8, 128.5, 128.4, 119.0, 117.1, 50.7, 36.7, 20.8. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₁₈N₃O: 304.1450; found: 304.1444.

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