Construction of Benzo-1,2,3-thiazaphosphole Heterocycles by Annulations of ortho-Phosphinoarenesulfonyl Fluorides with Trimethylsilyl Azide

Abstract

Annulations of ortho-phosphinoarenesulfonyl fluorides with trimethylsilyl azide were developed to access an unprecedented benzo-1,2,3-thiazaphosphole heterocycle. A corresponding reaction mechanism was proposed and further elucidated by experimental and computational studies. The reaction proceeds through a Staudinger-type iminophosphorane intermediate followed by intramolecular trapping with sulfonyl fluoride.

A Broad-Spectrum, Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates

“…Flash column chromatography was performed on 200-300 mesh silica gel (Huanghai, China). 2-(diphenylphosphanyl)-5-methylbenzenesulfonyl fluoride (1a), [1] 4-methylbenzenesulfonyl fluoride (1c), [2] 4-methoxybenzenesulfonyl fluoride (1e), [2] 2-methylbenzenesulfonyl fluoride (1f), [3] 4-(trifluoromethyl)benzenesulfonyl fluoride (1g), [3] 4-fluorobenzenesulfonyl fluoride (1h), [4] benzenesulfonyl fluoride (1i), [4] 4-(tert-butyl)benzenesulfonyl fluoride (1l), [2] naphthalene-1-sulfonyl fluoride (1m), [2] ((1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonyl fluoride (1n), [2] 4-methoxyphenyl fluorosulfate (4b), [5] 4-isopropylphenyl fluorosulfate (4d), [6] 4-iodophenyl fluorosulfate (4e), [7] 3,5-dimethylphenyl fluorosulfate (4f), [8] benzo [d] [1,3]dioxol-5-yl fluorosulfate (4g), [3] phenyl fluorosulfate (4h), [5] phenyl fluorosulfate, [3] 4-bromophenyl fluorosulfate (4i), [9] [1,1'biphenyl]-4-yl fluorosulfate (4j), [3] (8R,9S,13S,14S)-13-methyl-17-oxo- 7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4n), [10] (8R,9S,13S,14S,17R)-17-ethynyl-17-hydroxy-13-methyl- 7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl fluorosulfate (4o), [3] 3-nitrobenzenesulfonyl fluoride (8), [3] 4-(2-(pyrrolidin-1-yl)ethoxy)aniline (12), [11] 1H-benzo [d] [1,2,3]triazol-1-yl benzenesulfonate (16),…”

“…Instrumentation. 1 H, 19 F, 31 P and 13 C NMR spectra were recorded on a Bruker AVANCE III 400 MHz spectrometer at 298 K and referenced to residual protium in the NMR solvent (CDCl3, δ 7.26, CD3CN, 1.94 in 1 H NMR) and the carbon resonances of the solvent (CDCl3, δ 77.16, CD3CN, 1.32, 118.26 in 13 C NMR). Chemical shifts were reported in parts per million (ppm, δ) downfield from tetramethylsilane.…”

“…Rf = 0.10 (petroleum ether/ethyl acetate = 10/1, v/v). 1 H NMR (400 MHz, CDCl3)  7.41 (t, J = 7.8 Hz, 1H), 7.35 (app d, J = 7.8 Hz, 1H), 7.33 (app s, 1H),,…”

“…mp 134-136 C (chloroform). Rf =0.60 (ethyl acetate/methanol/ammonium hydroxide = 100/5/1, v/v) 1. H NMR (400 MHz, CDCl3)  8.16 (s, 1H), 8.12 (d, J = 8.3 Hz, 1H), 7.94 (s, 1H), 7.65 (d, J = 7.9 Hz, 1H), 7.50 (app t, J = 8.0 Hz, 1H), 7.36 (d, J = 8.9 Hz, 2H), 7.07 (br s, 1H), 6.86 (d, J = 8.9 Hz, 2H), 6.58 (br s, 1H), 4.10 (t, J = 6.0 Hz, 2H), 2.90 (t, J = 6.0 Hz, 2H), 2.702.54 (m, 4H), 2.13 (s, 3H), 1.871.73 (m, 4H…”

“…0.15 mL of this mixture was removed and diluted with CDCl3 (0.50 mL). The diluted mixture was transferred to an NMR tube and analyzed by 1 H NMR spectroscopy.A mixture of 1H-benzo[d][1,2,3]triazol-1-yl benzenesulfonate 16 (27.5 mg, 0.10 mmol), 1-amantadine 2d (15.1 mg, 1.0 equiv), 1,1,3,3-tetramethyldisiloxane (36 μL, 2.0 equiv), and DIPEA (35μL, 2.0 equiv) in NMP (0.50 mL) was stirred at 25 C in an aluminum heating block for 120 min. Then the mixture was diluted with CDCl3 (1.00 mL).…”