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DOI: 10.1055/s-2007-980344
Highly Stereoselective Cobalt-Catalyzed Allylation of Functionalized Diarylzinc Reagents
Publikationsverlauf
Publikationsdatum:
23. Mai 2007 (online)
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Abstract
Functionalized diarylzinc reagents react readily with allylic chlorides or phosphates in the presence of Co(acac)2 (10 mol%) to give the SN2 products in high yields and with retention of the double-bond configuration. Functionalities like ester, ketone, or cyano are tolerated.
Key words
catalysis - allylation - cobalt catalysis - organozinc reagents - stereoselective cross-coupling - nocarasin C
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2e For cobalt-catalyzed reactions involving organozinc reagents, see for example:
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References and Notes
Representative Procedure for the Preparation of ( E )-Ethyl 4-(3,7-Dimethylocta-2,6-dienyl)benzoate (3b): In a dry nitrogen-flushed Schlenk tube equipped with a septum and a magnetic stirring bar, ethyl 4-iodobenzoate (718 mg, 2.60 mmol) and anhyd Li(acac) (35 mg) were dissolved in anhyd NMP (3.0 mL) and cooled to 0 °C. Then, i-Pr2Zn (0.27 mL, 5.9 M solution in Et2O, 1.59 mmol, 0.6 equiv) was added dropwise. The reaction mixture was stirred at room temperature until the exchange reaction was complete (12 h). In a dry nitrogen-flushed Schlenk tube equipped with a septum and a magnetic stirring bar, geranyl chloride (173 mg, 1 mmol) and Co(acac)2 (27 mg, 10 mol%) were dissolved in anhyd NMP (0.5 mL) and cooled to 0 °C. The freshly prepared diarylzinc reagent (1.3 mmol) was added dropwise. The reaction mixture was stirred at 0 °C, until the reaction was complete (GC monitoring). Saturated aq NH4Cl was added, and the mixture was extracted several times with Et2O. The organic layer was dried (MgSO4) and the volatiles were removed in vacuo (the mixture was heated to 50 °C while evaporating under high vacuum for 2 h). Purification by flash column chromatography (eluent: pentane-Et2O, 98:2) afforded 3b as a pale yellow oil (205 mg 72%). 1H NMR (400 MHz, CDCl3): δ = 7.88 (d, J = 8.2 Hz, 2 H), 7.16 (d, J = 8.6 Hz, 2 H), 5.22-5.27 (m, 1 H), 5.00-5.04 (m, 1 H), 4.28 (q, J = 7.0 Hz, 2 H), 3.33 (d, J = 7.4 Hz, 2 H), 1.96-2.07 (m, 4 H), 1.63 (d, J = 1.2 Hz, 3 H), 1.61 (d, J = 1.2 Hz, 3 H), 1.53 (s, 3 H), 1.31 (t, J = 7.0 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 165.7, 146.2, 136.1, 130.5, 128.6, 127.2, 127.0, 123.1, 121.0, 59.7, 38.6, 33.2, 25.5, 24.7, 16.7, 15.1, 13.3. IR (neat): 2968, 2913, 1711, 1605, 1442, 1366, 1252, 1174, 1101, 1029, 769 cm-1. MS (EI): m/z (%) = 286 (8), 243 (16), 241 (24), 218 (22), 189 (22), 145 (61), 143 (31), 123 (81), 69 (100). HRMS (EI): m/z calcd for C19H26O2: 286.1933; found: 286.1922. ( E )-3-(3,7-Dimethylocta-2,6-di-enyl)benzonitrile (3c): 1H NMR (300 MHz, CDCl3): δ = 7.24-7.42 (m, 4 H), 5.17-5.26 (m, 1 H), 4.96-5.05 (m, 1 H), 3.30 (d, J = 7.1 Hz, 2 H), 1.94-2.12 (m, 4 H), 1.62 (s, 3 H), 1.61 (s, 3 H), 1.53 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 142.2, 136.8, 131.9, 130.8, 130.7, 128.5, 128.0, 123.0, 120.3, 118.1, 111.3, 38.6, 32.7, 25.4, 24.7, 16.7, 15.2. IR (neat): 3379, 2968, 2924, 2230, 1600, 1582, 1482, 1434, 1379, 1096, 792 cm-1. MS (EI): m/z (%) = 239 (1), 196 (4), 171 (6), 156 (7), 123 (24), 69 (100). HRMS (EI): m/z calcd C17H21N: 239.1674; found: 239.1661. ( E )-1-(3,7-Dimethylocta-2,6-dienyl)-3-trifluoromethylbenzene (3d): 1H NMR (600 MHz, CDCl3): δ = 7.38-7.43 (m, 2 H), 7.31-7.37 (m, 2 H), 5.28-5.33 (m, 1 H), 5.06-5.11 (m, 1 H), 3.41 (d, J = 7.6 Hz, 2 H), 2.05-2.18 (m, 4 H), 1.72 (d, J = 1.0 Hz, 3 H), 1.68 (s, 3 H), 1.60 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 142.9, 137.5, 131.9, 131.8, 130.8 (q, J = 32.5 Hz), 128.9, 125.5 (q, J = 272.6 Hz), 125.2 (m), 124.2, 122.8 (m), 122.2, 39.9, 34.2, 26.7, 25.8, 17.9, 16.5. IR (neat): 2968, 2913, 1442, 1366, 1328, 1156, 1115, 824, 631 cm-1. MS (EI): m/z (%) = 282 (2), 239 (5), 159 (6), 123 (25), 69 (100). HRMS (EI): m/z calcd for C17H21F3: 282.1595; found: 282.1608. ( E )-1-Bromo-2-(3,7-dimethylocta-2,6-di-enyl)benzene (3e): 1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 7.4 Hz, 1 H), 7.21-7.24 (m, 2 H), 7.02-7.08 (m, 1 H), 5.27-5.33 (m, 1 H), 5.08-5.14 (m, 1 H), 3.45 (d, J = 7.4 Hz, 2 H), 2.04-2.17 (m, 4 H), 1.71 (d, J = 0.8 Hz, 3 H), 1.69 (d, J = 1.2 Hz, 3 H), 1.61 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 141.1, 137.5, 132.8, 131.8, 130.2, 127.6, 127.6, 124.9, 124.4, 121.5, 40.0, 34.8, 26.8, 26.0, 18.0, 16.5. IR (neat): 2968, 2913, 1604, 1500, 1442, 1366, 1101, 769 cm-1. MS (EI): m/z (%) = 294 (2), 292 (2), 251 (9), 249 (9), 145 (17), 144 (87), 143 (23), 129 (47), 128 (19), 123 (100), 69 (78). HRMS (EI): m/z calcd for C16H21Br: 292.0827; found: 292.0831. ( E )-1-(3,7-Dimethylocta-2,6-di-enyl)naphthalene (3f): 1H NMR (300 MHz, CDCl3): δ = 7.92-7.98 (m, 1 H), 7.73-7.80 (m, 1 H), 7.63 (d, J = 7.4 Hz, 1 H), 7.38-7.47 (m, 2 H), 7.23-7.36 (m, 2 H), 5.30-5.38 (m, 1 H), 4.98-5.07 (m, 1 H), 3.71 (d, J = 6.7 Hz, 2 H), 1.95-2.11 (m, 4 H), 1.71 (d, J = 1.5 Hz, 3 H), 1.58 (s, 3 H), 1.51 (s, 3 H). 13C NMR (75 MHz, CDCl3): δ = 138.0, 136.6, 134.1, 132.4, 131.7, 128.9, 126.8, 125.9, 125.9, 125.8, 125.7, 124.5, 124.3, 123.1, 40.0, 31.9, 26.9, 25.9, 18.0, 16.5. IR (neat): 3045, 2966, 2913, 2853, 1597, 1510, 1440, 1396, 1376, 790 cm-1. MS (EI): m/z (%) = 264 (37), 196 (18), 195 (98), 193 (33), 181 (24), 167 (45), 166 (42), 165 (99), 153 (100), 141 (59), 123 (85), 69 (51). HRMS (EI): m/z calcd for C20H24: 264.1878; found: 264.1886.