methyl (E)-4-oxo-4-phenylbut-2-enoate

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 268 mg of methyl β-benzoyl-α-methoxypropionate, 150 mg of paratoluenesulfonic acid monohydrate and 5 ml of toluene was stirred at 80° C. for 1 hour. A pressure was reduced with an aspirator and a total amount of the resultant was reduced to 1/2 by concentration. The resultant was stirred at 80° C. for 20 minutes and was left for cooling. The reaction mixture was distributed between ethyl acetate and water and the ethyl acetate layer was washed with a saturated solution of NaHCO3 and then with water, and was dried with anhydrous magnesium sulfate. The solvent was distilled away to give 206 mg of methyl trans-β-benzoylacrylate as a yellow oil. a total amount of the resultant was reduced to 1/2 by concentration The resultant was stirred at 80° C. for 20 minutes was left for cooling the ethyl acetate layer was washed with a saturated solution of NaHCO3 with water, and was dried with anhydrous magnesium sulfate The solvent was distilled away

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

Procedure: Prepared according to the general procedure from 3-(tert-butyldimethylsilyloxy)-2-chloropropanal and (E)-methyl 4-oxo-4-phenylbut-2-enoate using 0.5 mol % 1 as the catalyst in 80% yield as a 3:1 mixture of diastereomers. The diastereomers were separated by silica gel chromatography (15:1 hexanes/EtOAc) and characterized separately. [α]D20 (c 1.07, CHCl3)=+133.6; 1H NMR (400 MHz, CDCl3) δ 7.65-7.62 (m, 2H), 7.40-7.37 (m, 3H), 5.94 (d, 1H, J=7.1 Hz), 4.26 (dd, 1H, J=10.6, 5.7 Hz), 3.88 (t, 1H, J=10.1 Hz), 3.76 (dd, 1H, J=13.7, 7.4 Hz), 3.72 (s, 3H), 3.08-3.02 (m, 1H), 0.89 (s, 9H), 0.07 (s, 3H), 0.06 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 170.9, 167.7, 152.5, 131.9, 129.8, 128.8, 125.0, 98.1, 59.7, 52.6, 42.5, 38.7, 25.9, 18.4, −5.4, −5.6; IR (thin film) ν 3062, 2953, 2929, 2886, 2857, 1778, 1739, 1254, 1197, 1176 cm−1; HRMS (EI) calcd for C20H25O5Si [M]+ 376.1706, found 376.1697; 97% ee (3R,4S)-isomer as determined by HPLC (AD-H, 100:1 hexanes/i-PrOH), tr (3R,4S)=21.8 min, tr (3S,4R)=15.2 min. Prepared The diastereomers were separated by silica gel chromatography (15:1 hexanes/EtOAc) as determined by HPLC (AD-H, 100:1 hexanes/i-PrOH), tr (3R,4S)=21.8 min, tr (3S,4R)=15.2 min.

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

Procedure: Prepared according to the general procedure from 2-chlorododecanal and (E)-methyl 4-oxo-4-phenylbut-2-enoate using 0.5 mol % 1 as the catalyst in 90% yield as a single diastereomer (white solid). [α]r)20 (c 1.15, CHCl3)=+154.3; mp=108-111° C.; 1H NMR (400 MHz, CDCl3) δ 7.66-7.63 (m, 2H), 7.40-7.37 (m, 3H), 5.89 (d, 1H, J=6.4 Hz), 3.73 (s, 3H), 3.57 (t, 1H, J=6.3 Hz), 2.76 (q, 1H, J=6.3 Hz), 2.04 (t, 1H, J=7.0 Hz), 1.47-1.26 (m, 18H), 0.88 (t, 3H, J=6.8 Hz); 13C NMR (100 MHz, CDCl3) δ 171.0, 169.5, 152.4, 132.0, 129.8, 128.8, 125.0, 97.9, 52.7, 41.9, 40.7, 32.1, 29.8, 29.8, 29.6, 29.6, 27.4, 27.3, 22.9, 14.4; IR (thin film) ν 3062, 2916, 2846, 1758, 1722, 1464, 1339, 1176, 1115 cm−1; HRMS (ESI) calcd for C23H32O4 [M+Na]+ 395.2192, found 395.2192; 99% ee (3S,4S)-isomer as determined by HPLC (AD-H, 9:1 hexanes/i-PrOH), tr (3S,4S)=7.2 min, tr (3R,4R)=10.3 min. Prepared

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

Procedure: Prepared according to the general procedure from 2-chloro-hydrocinnamaldehyde and (E)-methyl 4-oxo-4-phenylbut-2-enoate using 0.5 mol % 1 as the catalyst in 91% yield as a 8:1 mixture of diastereomers (white solid). [α]D20 (c 1.16, CHCl3)=+130.4; mp=103-106° C.; 1H NMR (400 MHz, CDCl3) δ 7.67-7.61 (m, 2H), 7.41-7.27 (m, 6H), 7.27-7.17 (m, 2H), 5.82 (d, 1H, J=7.0 Hz), 5.75* (d, 1H, J=5.7 Hz), 3.77 (s, 3H), 3.69* (s, 3H), 3.61-3.58* (m, 1H), 3.56 (dd, 1H, J=14.3, 4.6 Hz), 3.42-3.37* (m, 1H), 3.32-3.28 (m, 1H), 3.17* (dd, 1H, J=13.8, 5.7 Hz), 3.04-2.99 (m, 1H), 2.92* (dd, 1H, J=13.8, 9.2 Hz), 2.77 (dd, 1H, J=14.3, 10.1 Hz); 13C NMR (100 MHz, CDCl3) δ 170.8, 168.9, 152.6, 138.2, 131.8, 129.8, 129.4, 129.2, 129.0, 128.8, 127.4, 127.1, 125.0, 98.1, 95.9, 52.9, 52.8, 42.8, 42.3, 41.2, 40.6, 35.5, 33.4; IR (thin film) ν 3061, 3028, 2952, 1777, 1733, 1496, 1448, 1173, 1069 cm−1; HRMS (ESI) calcd for C20H18O4 [M+Na]+ 345.1097, found 345.1094; >99% ee (3S,4S)-isomer as determined by HPLC (AD-H, 9:1 hexanes/i-PrOH), tr (3S,4S)=32.4 min, tr (3R,4R)=20.3 min. Prepared

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 268 mg of methyl β-benzoyl-α-methoxypropionate, 150 mg of paratoluenesulfonic acid monohydrate and 5 ml of toluene was stirred at 80° C. for 1 hour. A pressure was reduced with an aspirator and a total amount of the resultant was reduced to 1/2 by concentration. The resultant was stirred at 80° C. for 20 minutes and was left for cooling. The reaction mixture was distributed between ethyl acetate and water and the ethyl acetate layer was washed with a saturated solution of NaHCO3 and then with water, and was dried with anhydrous magnesium sulfate. The solvent was distilled away to give 206 mg of methyl trans-β-benzoylacrylate as a yellow oil. a total amount of the resultant was reduced to 1/2 by concentration The resultant was stirred at 80° C. for 20 minutes was left for cooling the ethyl acetate layer was washed with a saturated solution of NaHCO3 with water, and was dried with anhydrous magnesium sulfate The solvent was distilled away