1-phenylhex-5-en-3-ol

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a round-bottomed flask containing 1-phenyl-hex-5-en-3-ol (43 mg, 0.24 mmol, 1 eq)) in DCM (2 mL) was added allyltriisopropylsilane (0.173 mL, 0.72 mmol, 3 eq). Hoveyda-Grubbs' Catalyst (4 mg, 0.006 mmol, 0.025 eq) was subsequently added as a solid and the reaction was left to stir under an atmosphere of argon. After 6 days the reaction was concentrated under reduced pressure to a dark brown oil. Column chromatography (hexane:ether, 100:0, 90:10, 85:15) gave 1-phenyl-7-(triisopropylsilyl)hept-5-en-3-ol as a colourless oil (51 mg, 61% yield). For major isomer E: 1H NMR (400 MHz, CDCl3) δ 1.05 (s, 21H, Si(i−Pr)3), 1.60-1.62 (d, 2H, CH2 Si(i−Pr)3, J=8 Hz), 1.72-1.85 (m, 2H, CH2CH2CHOH), 2.06-2.14 (m, 1H, CHOHCH2CH), 2.22-2.34 (m, 1H, CHOHCH2CH), 2.64-2.74 (m, 1H, PhCH2), 2.78-2.87 (m, 1H, PhCH2), 3.58-3.64 (m, 1H, CHOH), 5.24-5.34 (m, 1H, CH2CHCH), 5.58-5.66 (dt, 1H, CH2CHCH, J=16, 8 Hz), 7.17-7.23 (m, 4H, Ph), 7.27-7.31 (m, 1H, Ph); 13C NMR (100 MHz, CDCl3) δ 11.0 (Si(i−Pr)3), 15.6 (CH2 Si(i−Pr)3), 18.7 (Si(i−Pr)3), 32.1 (PhCH2), 38.4 (PhCH2CH2), 41.1 (CHOHCH2), 70.4 (CHOH), 123.9 (CH2CHCH), 125.7 (Ph), 128.3 (Ph), 128.4 (Ph), 131.9 (CH2CHCH), 142.2 (Ph). For minor isomer Z: 1H NMR (400 MHz, CDCl3) δ 1.05 (s, 21H, Si(i−Pr)3), 1.60-1.62 (d, 2H, CH2 Si(i−Pr)3, J=8 Hz), 1.72-1.85 (m, 2H, CH2CH2CHOH), 2.06-2.14 (m, 1H, CHOHCH2CH), 2.22-2.34 (m, 1H, CHOHCH2CH), 2.64-2.74 (m, 1H, PhCH2), 2.78-2.87 (m, 1H, PhCH2), 3.65-3.71 (m, 1H, CHOH), 5.24-5.34 (m, 1H, CH2CHCH), 5.68-5.75 (dt, 1H, CH2CHCH, J=12, 8 Hz), 7.17-7.23 (m, 4H, Ph), 7.27-7.31 (m, 1H, Ph); 13C NMR (100 MHz, CDCl3) δ 11.0 (Si(i−Pr)3), 15.6 (CH2 Si(i−Pr)3), 18.7 (Si(i−Pr)3), 32.1 (PhCH2), 35.3 (CHOHCH2), 38.4 (PhCH2CH2), 70.9 (CHOH), 122.3 (CH2CHCH), 125.7 (Ph), 128.3 (Ph), 128.4 (Ph), 130.3 (CH2CHCH), 142.2 (Ph); IR (v, cm−1) 3362 (OH), 3026 (Ar—H), 1604 (C═C), 1496 (Ar), 1462 (Ar), 699 (Si—C); HRMS required for C22H38OSi: 346.2692, found 346.2683. the reaction was left After 6 days the reaction was concentrated under reduced pressure to a dark brown oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a round-bottomed flask containing 1-phenyl-hex-5-en-3-ol (495 mg, 2.8 mmol, 1 eq) in DCM (12 mL) was added allyltrimethylsilane (1.79 mL, 11.2 mmol, 4 eq). Hoveyda-Grubbs' Catalyst (44 mg, 0.07 mmol, 0.025 eq) was subsequently added as a solid and left to stir at room temperature under an atmosphere of argon. After 72 hours a further equivalent of allyltrimethylsilane was added (0.445 mL, 2.78 mmol). After 7 days the reaction mixture was concentrated under reduced pressure to a dark brown oil. Column chromatography (hexane:ether, 100:0, 9:1, 85:15) gave 1-phenyl-7-(trimethylsilyl)-hept-5-en-3-ol as a colourless oil (445 mg, 61% yield). For major isomer E: 1H NMR (400 MHz, CDCl3) δ 0.006 (s, 9H, SiMe3), 1.47-1.49 (d, 2H, CH2SiMe3, J=8 Hz), 1.74-1.84 (mn, 2H, CH2CH2CHOH), 2.06-2.14 (m, 1H, CHOHCH2CH), 2.20-2.31 (m, 1H, CHOHCH2CH), 2.66-2.74 (m, 1H, PhCH2), 2.79-2.86 (m, 1H, PhCH2), 3.57-3.63 (m, 1H, CHOH), 5.21-5.28 (dt, 1H, CH2CHCH, J=15.2 Hz, 8 Hz), 5.50-5.58 (dt, 1H, CH2CHCH, J=15.2 Hz, 8 Hz), 7.18-7.24 (m, 3H, Ph), 7.27-7.31 (m, 2H, Ph); 13C NMR (100 MHz, CDCl3) δ −2.0 (SiMe3), 23.0 (CH2SiMe3), 32.1 (PhCH2), 38.3 (PhCH2CH2), 41.0 (CHOHCH2), 70.2 (CHOH), 123.8 (CHCH), 125.7 (Ph), 128.4 (Ph), 130.9 (CHCH), 142.2 (Ph). For minor isomer Z: 1H NMR (400 MHz, CDCl3) δ 0.012 (s, 9H, SiMe3), 1.47-1.49 (d, 2H, CH2SiMe3, J=8 Hz), 1.74-1.84 (m, 2H, CH2CH2CHOH), 2.06-2.14 (m, 1H, CHOHCH2CH), 2.20-2.31 (m, 1H, CHOHCH2CH), 2.66-2.74 (m, 1H, PhCH2), 2.79-2.86 (m, 1H, PhCH2), 3.64-3.69 (m, 1H, CHOH), 5.30-5.35 (dt, 1H, CH2CHCH, J=10.4 Hz, 8 Hz), 5.61-5.66 (dt, 1H, CH2CHCH, J=10.4 Hz, 8 Hz), 7.18-7.24 (m, 3H, Ph), 7.27-7.31 (m, 2H, Ph); 13C NMR (100 MHz, CDCl3) δ −1.82 (SiMe3), 18.7 (CH2SiMe3), 32.1 (PhCH2), 31.5 (CHOHCH2), 38.4 (PhCH2CH2), 70.8 (CHOH), 122.4 (CHCH), 125.7 (Ph), 128.3 (Ph), 129.3 (CHCH), 142.1 (Ph); IR (v, cm−1) 3383 (OH), 3063 (ArH), 1667 (C═C), 1604 (Ar), 1496 (Ar), 850 (Si—C). MS (GCT, CI+) m/z 280.2101 [M+NH4]+ HRMS required for C16H26OSiNH4: 280.2097, found 280.2101. left After 7 days the reaction mixture was concentrated under reduced pressure to a dark brown oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of 3-phenylpropionaldehyde (1.06 mL, 8 mmol, 1 eq) and activated zinc (628 mg, 9.6 mmol, 1.2 eq) in THF (3.2 mL) at 0° C. was added one drop of allyl bromide. After the reaction was initiated, the remaining allyl bromide (total 0.831 mL, 9.6 mmol, 1.2 eq) was added slowly. The contents were stirred overnight at room temperature. After 20 hours the reaction was quenched with saturated aq. NH4Cl solution (15 mL), extracted with ether (3×20 mL) and the combined organic phases washed with brine (15 mL). The organic layer was dried over MgSO4 and the solvent was removed under reduced pressure to give crude 1-phenyl-hex-5-en-3-ol as a yellow oil. Column chromatography (hexane:ether, 85:15, 80:20, 75:25) gave a colourless oil, (966 mg, 69% yield). 1H NMR (400 MHz, CDCl3) δ 1.80-1.85 (m, 3H, CCH2CH2, +COH), 2.19-2.26 (m, 1H, CHOHCH2CH), 2.33-2.39 (m, 1H, CHOHCH2CH) 2.69-2.76 (m, 1H, PhCH2CH2), 2.82-2.89 (m, 1H, PhCH2CH2), 3.69-3.74 (m, 1H, CHOH), 5.16-5.19 (s, 1H, CHCH2 (cisH)), 5.19-5.20 (d, 1H, CHCH2 (trans H)), 7.21-7.26 (m, 3H, PhCH2), 7.30-7.34 (m, 2H, PhCH2); 13C NMR (100 MHz, CDCl3) δ 32.0 (PhCH2CH2), 38.4 (CH2CH2CH), 42.0 (CHOHCH2CH), 69.9 (CHOH), 118.1 (CHCH2), 125.7 (Ph), 128.4 (Ph), 128.5 (Ph), 134.6 (CHCH2), 142.0 (Ph); IR (v, cm−1) 3385 (OH), 3027 (Ar), 2932 (CH2), 1641 (CH═CH2), 1496 (Ph), 916 (CH═CH2); MS (GCT, CI+) m/z 194.2 [M+NH4]+ HRMS required for C12H20NO: 194.1545, found 194.1543. After 20 hours the reaction was quenched with saturated aq. NH4Cl solution (15 mL) extracted with ether (3×20 mL) the combined organic phases washed with brine (15 mL) The organic layer was dried over MgSO4 the solvent was removed under reduced pressure to give crude 1-phenyl-hex-5-en-3-ol as a yellow oil