Brønsted Acid Catalyzed Amination of 1,3-Dicarbonyl Compounds by Iminoiodanes

Ciputra Tejo; Hui Quan Yeo; Philip Wai Hong Chan

doi:10.1055/s-0033-1340108

Synlett, Table of Contents

Synlett 2014; 25(2): 201-204
DOI: 10.1055/s-0033-1340108

letter

Brønsted Acid Catalyzed Amination of 1,3-Dicarbonyl Compounds by Iminoiodanes

Ciputra Tejo

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 Email: waihong@ntu.edu.sg

,

Hui Quan Yeo

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 Email: waihong@ntu.edu.sg

,

Philip Wai Hong Chan*

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore Fax: +6567911961 Email: waihong@ntu.edu.sg

› Author Affiliations

Abstract

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Abstract

A synthetic method to aminate 1,3-dicarbonyl compounds with PhI=NTs using Brønsted acid catalysis is described herein. The method was shown to be applicable to β-keto esters and phosphonates as well as 1,3-diones, providing the corresponding α,α-acyl amino acid derivatives in moderate to excellent yields.

Key words

α,α-acyl amino acid derivatives - iminoiodanes - amination - Brønsted acid catalysis - 1,3-dicarbonyl compounds

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References

References and Notes

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7 General Procedure To a degassed mixture of PhI=NTs (0.6 mmol, 224 mg) and powdered 4 Å MS (240 mg) was added CH₂Cl₂ (1 mL). The reaction was cooled to 0 °C, and a solution of TFA (0.05 mmol, 3.83 μL) in CH₂Cl₂ (1 mL) was added. The 1,3-dicarbonyl compound was added, and the reaction was monitored by TLC analysis. Upon completion, the reaction mixture was filtered, washed with EtOAc (40 mL), concentrated under reduced pressure, and purified by flash chromatography [n-hexane–EtOAc (4:1) as eluent] to furnish the title compound.
8 Representative Experimental Data Ethyl 2-(4-Methylphenylsulfonamido)-3-oxo-3-phenylpropanoate (2a) Reaction time = 1.5 h; yield 86%; 0.162 g; white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.98 (d, J = 7.4 Hz, 2 H), 7.73 (d, J = 8.3 Hz, 2 H), 7.62 (t, J = 7.4 Hz, 1 H), 7.47 (t, J = 7.7 Hz, 2 H), 7.24 (d, J = 8.1 Hz, 2 H), 6.00 (d, J = 8.9 Hz, 1 H), 5.58 (d, J = 8.9 Hz, 1 H), 3.97 (q, J = 7.1 Hz, 2 H), 2.38 (s, 3 H), 1.04 (t, J = 7.1 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 190.2, 165.9, 144.1, 144.0, 136.6, 134.7, 129.8, 129.5, 128.9, 127.4, 62.6, 60.9, 21.6, 13.8. Ethyl 3-(4-Bromophenyl)-2-(4-methylphenyl-sulfonamido)-3-oxopropanoate (2h) Reaction time = 1.5 h; yield 60%; 0.114 g; white solid. ¹H NMR (400 MHz, CDCl₃): δ = 7.86 (d, J = 7.2 Hz, 2 H), 7.72 (d, J = 8.3 Hz, 2 H), 7.62 (d, J = 8.7 Hz, 2 H), 7.25 (d, J = 8.2 Hz, 2 H), 5.96 (d, J = 8.7 Hz, 1 H), 5.52 (d, J = 8.7 Hz, 1 H), 4.02–3.93 (m, 2 H), 2.39 (s, 3 H), 1.05 (t, J = 7.2 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 189.6, 165.9, 144.2, 136.5, 132.3, 130.9, 130.2, 129.8, 127.4, 62.9, 60.9, 21.6, 13.8. N-(2,4-Dioxopentan-3-yl)-4-methylbenzenesulfonamide (2s) Reaction time = 2 h; yield 62%; 0.0840 g; yellow solid. ¹H NMR (300 MHz, CDCl₃): δ = 16.3 (s, 1 H), 7.84 (s, 1 H), 7.71 (d, J = 8.1 Hz, 2 H), 7.32 (d, J = 8.1 Hz, 2 H), 6.16 (s, 1 H), 5.16 (s, 1 H), 2.44 (s, 3 H), 1.87 (s, 6 H). ¹³C NMR (75 MHz, CDCl₃): δ = 194.1, 144.3, 136.6, 130.1, 127.4, 110.1, 22.1, 21.6.

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