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General Procedure for the Preparation of α- Chlorobenzylphosphonates from α-Hydroxyphosphonates A solution of 1k (1.00 g, 3.46 mmol, 1.0 equiv) and Ph3P (1.36 g, 5.19 mmol, 1.5 equiv) in dry CCl4 (10 mL) is refluxed for 8 h under argon. Then, the mixture is evaporated under reduced pressure, and the semisolid residue is extracted with PE. The combined extracts are filtered, and the solvent is removed under reduced pressure. The crude material was purified by flash column chromatography on silica gel to yield 3k as yellow oil (0.81 g, 76, 1H NMR (300 MHz, CDCl3, δ, 1.26 (t, J, 7.0 Hz, 3 H, 1.35 (t, J, 7.0 Hz, 3 H, 4.00-4.14 (m, 2 H, 4.15-4.28 (m, 2 H, 5.00 (d, 2JPH, 15.2 Hz, 1 H, 7.73 (d, J, 8.6 Hz, 2 H, 8.25 (d, J, 8.6 Hz, 2 H) ppm. 13C NMR (75 MHz, CDCl3, δ, 16.2 d, 3JPC
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PC = 7.0 Hz), 123.6, 129.8, 141.4, 148.0 ppm.
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68949108928
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General Procedure for the Preparation of α,α- Chlorofluorobenzylphosphonates from α-Chlorophosphonates To a solution of the α-chlorophosphonates 3k (0.31 g, 0.94 mmol, 1.0 equiv) in dry THF (10 mL) at -78°C was added dropwise a solution of NaHMDS (1.69 mmol, 2.0 M in THF, 1.5 equiv) in dry THF (5 mL) under argon. The resulting dark green solution was stirred for 1 h at -78°C. A solution of NFSI (0.41 g, 1.31 mmol, 1.3 equiv) in dry THF (5 mL) was added over a period of 10 min. After addition, the solution was stirred for 1 h and then allowed to warm to -30°C. The reaction was quenched with 0.01 N HC1, and the resulting solution was extracted with CH2Cl2. The combined organic layer was dried over MgSO4, and the solvent was removed under reduced pressure. The crude material was purified via flash column chromatography on silica gel to yield 4k as yellow oil (0.24 g, 77, 1H NMR 300 MHz
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PF = 88.1 Hz) ppm.
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We thank one of the reviewers for pointing out these possibilities
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We thank one of the reviewers for pointing out these possibilities.
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