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58149185695
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Typical Experimental Procedure. A flame-dried, 50 mL flask was purged with nitrogen and charged with diethyl (chloromethyl)phosphonate 4b (4.0 mmol, 746 mg, 1.0 equiv) and dry THF (20 mL, The solution was cooled below-90°C (liquid nitrogen/ethanol bath, and n-butyllitium (1.6 M solution in hexane, 2.5 mL, 4.0 mmol, 1.0 equiv) was added slowly by syringe followed by Bu 3B (1.0 M solution in diethyl ether, 4.0 mL, 1.0 equiv) in one portion. The reaction mixture was warmed slowly to room temperature and was quenched by addition of water. The resulting biphasic mixture was stirred at rellux lor 2 h. After being cooled to room temperature, the layers were separated, the aqueous phase was extracted with EtOAc (3 ×, the combined organic layers were dried with MgSO4, and solvents were removed in vacuo. Purification of the crude product by flash chromatography on silica gel (EtOAc/hexane 1:1. v/v) yielded diethyl pentylphosphonate 3b H 3.84 mmol, 800
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4, and solvents were removed in vacuo. Purification of the crude product by flash chromatography on silica gel (EtOAc/hexane 1:1. v/v) yielded diethyl pentylphosphonate 3b H (3.84 mmol, 800 mg, 96%). Additional details can be found in the Supporting Information.
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21
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58149182857
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Detailed procedures for the preparation of the reagents 4 can be found in the Supporting Information.
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Detailed procedures for the preparation of the reagents 4 can be found in the Supporting Information.
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24
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46149129231
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Teulade, M. P.; Savignac, P.; Abouajouade, E.; Collignon, N. J. Organomet. Chem. 1986, 312. 283. See also ref 4b.
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For a review on phosphine- borane complexes, see
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For references on the conversion of C-B into C-I, sec: (a) Montchamp, J.-L.; Migaud, M. E.; Frost. J. W. J. Org. Chem. 1993, 58, 7679.
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For references on the conversion of C-B into C-I, sec: (a) Montchamp, J.-L.; Migaud, M. E.; Frost. J. W. J. Org. Chem. 1993, 58, 7679.
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For references on the use of secondary a-iodophosphonates, see: a
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For references on the use of secondary a-iodophosphonates, see: (a) Balczewski, P.; Szadowiak, A.; Bodzioch, A.; Bialas, T.; Wieczorek, W. M.; Szyrej, M. J. Organomet. Chem. 2007, 692, 997.
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