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DOI: 10.1055/s-2007-991094
Reaction of 1-Cyclopropylallenes with Phenylselenyl Bromide: A Highly Efficient and Stereoselective Method for the Preparation of 2-Phenylselenyl-6-bromo-1,3-hexadienes
Publication History
Publication Date:
12 October 2007 (online)

Abstract
Reaction of 1-cyclopropylallenes with phenylselenyl bromide, which provided a highly efficient and stereoselective method for the preparation of 2-phenylselenyl-6-bromo-1,3-hexadienes, was investigated.
Key words
cyclopropyl - allene - selenium - 1,3-hexadiene - ionic reaction
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References and Notes
Preparation of 2-Phenylselenyl-3-phenyl-6-bromo-1,3-hexadiene (9a); Typical Procedure: 1-Phenyl-1-cyclopropylallene (3a; 0.33 mmol) was first dissolved in CH2Cl2 (1 mL) and the reaction was kept at 0 °C under ice-bath cooling. Under a nitrogen atmosphere protection, a solution of phenylselenyl bromide (0.3 mmol) in CH2Cl2 (6 mL) was slowly added. The reaction proceeded very rapidly and the color of phenylselenyl bromide disappeared immediately. The reaction liquid was stirred for an extra 1 min. Then, the solvent was evaporated under vacuum and the residue was separated by preparation TLC (eluent: PE) to give 9a in 78% yield. The other 2-phenylselenyl-6-bromo-1,3-hexadienes could be prepared in the similar way. Selected Data of 9a: IR (film): 3056, 3024, 1597, 1440, 1126, 882, 762, 740, 694 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.29-7.55 (m, 10 H), 5.88 (t, J = 6.8 Hz, 1 H), 5.63 (s, 1 H), 5.53 (s, 1 H), 3.32 (t, J = 7.2 Hz, 2 H), 2.78-2.83 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 32.2, 33.0, 118.2, 126.6, 126.9, 127.6, 127.9, 128.2, 128.6, 129.0, 136.6, 138.7, 139.8, 142.9. MS (EI, 70 eV): m/z (%) = 392 (26) [M+], 236 (22), 155 (100). HRMS (EI): m/z calcd for C18H17SeBr: 391.9679; found: 391.9675.
9Spectral Data of Compound 11: IR (film): 2973, 2924, 1441, 1068, 1025, 740, 699 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.28-7.59 (m, 10 H), 6.01 (s, 1 H), 5.09 (s, 1 H), 3.67-3.79 (m, 2 H), 1.54-1.57 (m, 1 H), 1.35 (t, J = 6.8 Hz, 3 H), 0.43-0.55 (m, 2 H), 0.14-0.24 (m, 2 H). 13C NMR (100 MHz, CDCl3): δ = 0.7, 3.5, 15.7, 16.6, 58.4, 85.7, 115.1, 127.2, 127.3, 127.8, 128.2, 129.2, 129.3, 136.7, 140.0, 152.1. MS (EI, 70 eV): m/z (%) = 358 (5) [M+], 317 (26), 105 (100). HRMS (EI): m/z calcd for C20H22OSe: 358.0836; found: 358.0844.