N-Triflylphosphorimidoyl Trichloride: A Versatile Reagent for the Synthesis of Strong Chiral Brønsted Acids

Abstract

A series of strong Brønsted acids has been synthesized in high yields using N-triflylphosphorimidoyl trichloride as reagent. The syntheses proceed efficiently with electron-rich, electron-deficient, and sterically hindered substrates.

Key words

N-triflylphosphorimidoyl trichloride - Brønsted acid - N-triflylphosphoramide - N-triflylthiophosphoramide - N,N′-bis(triflyl)phosphoramidimidate

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• 9 General Procedure: In a flame-dried vial under Ar, the corresponding (S)- or (R)-BINOL (1.0 equiv) was dissolved in anhyd CH₂Cl₂ (0.20 M). TfNPCl₃ (1.1 equiv) and DIPEA (5.0 equiv) were added and the mixture was stirred for 10 min at ambient temperature. After the full consumption of the starting material (as indicated by TLC), the second nucleophile was added (20 μL for H₂O, 2.0 equiv for H₂S and TfNH₂). After an additional 10 min of stirring, the reaction mixture was dried over Na₂SO₄, filtered, concentrated, and purified by column chromatography on silica gel to afford the desired product as a salt. Acidification in CH₂Cl₂ with HCl (3.0 M) followed by drying under reduced pressure afforded the desired product as a free acid.
• 10 Spectroscopic Data of (S)-6a: ¹H NMR (501 MHz, CD₂Cl₂): δ = 8.14 (s, 1 H), 8.09 (s, 1 H), 8.05 (dd, J = 8.4, 1.1 Hz, 1 H), 8.00 (dd, J = 8.2, 1.1 Hz, 1 H), 7.67–7.72 (m, 2 H), 7.60 (ddt, J = 10.4, 6.0, 1.9 Hz, 3 H), 7.48 (dd, J = 8.4, 7.0 Hz, 2 H), 7.39 (m, 7 H), 7.29 (dd, J = 8.6, 1.1 Hz, 1 H), 7.22 (ddd, J = 8.4, 6.7, 1.3 Hz, 1 H). ¹³C NMR (126 MHz, CD₂Cl₂): δ = 143.53 (d, J = 11.7 Hz), 142.73 (d, J = 9.4 Hz), 136.01, 135.98, 133.55, 133.53, 133.36, 133.34, 131.96, 131.93, 131.83, 131.80, 130.00, 129.71, 128.54, 128.53, 128.47, 128.11, 128.09, 127.87, 126.95, 126.94, 126.79, 126.69, 126.62, 126.38, 122.21 (d, J = 2.0 Hz), 122.19 (d, J = 3.0 Hz), 118.71 (qd, J = 322.1, 1.6 Hz). ¹⁹F NMR (471 MHz, CD₂Cl₂): δ = –77.8. ³¹P NMR (203 MHz, CD₂Cl₂): δ = –5.8. HRMS (ESI): m/z [M – H⁺] calcd for C₃₃H₂₀F₃NO₅PS: 630.0757; found: 630.0759.