methyl [(E)-3-phenylprop-2-enyl] carbonate

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

Procedure: To a solution of Methyl (2E)-3-phenylprop-2-en-1-yl carbonate (1.5 g) in THF (25 ml), was added N,N-bis[(1S)-1-phenylethyl]dinaphtho[1,2-f:2′,1′-d][1,3,2]dioxaphosphepin-4-amine (420 mg), and chloro(1,5-cyclooctadiene)iridium(I) dimer (105 mg) at RT under N2. The mixture was heated at reflux overnight. Evaporated material then redissoled in a 50:50 mixture of EtOH:THF. To this solution was added macro porous p-toluenesulfonic acid resin (10 g) and the mixture was gently agitated for 3 h. At this time the resin was washed completely with THF, THF:EtOH and EtOH. To a suspension of the resin in MeOH (75 ml) was added 7 N NH3.MeOH (75 ml). This mixture was gently agitated for 2 hours and filered, washing with MeOH, THF, THF:MeOH, and DCM. Evaporating this filtrate left a yellow oil (1.2 g). This oil was then distilled on a kuglerohr vacumme distilation aparatus. This left the title compound as a clear oil. (830 mg, 53%). 1H NMR (300 MHz, CDCl3) δ 0.90 (d, 6H, J=6.6 Hz), 1.64-1.81 (m, 1H), 2.18-2.45 (m, 2H), 4.15 (d, 1H, J=6.9 Hz), 5.06-5.22 (m, 2H), 5.85-5.97 (m, 1H), 7.20-7.41 (m, 5H). The mixture was heated at reflux overnight At this time the resin was washed completely with THF, THF To a suspension of the resin in MeOH (75 ml) was added 7 N NH3 This mixture was gently agitated for 2 hours washing with MeOH, THF, THF Evaporating this filtrate left a yellow oil (1.2 g) This oil was then distilled on a kuglerohr vacumme distilation aparatus This left the title compound as a clear oil

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

Procedure: To a solution of Methyl (2E)-3-phenylprop-2-en-1-yl carbonate (384 mg) in THF (5 ml), was added N,N-bis[(1S)-1-phenylethyl]dinaphtho[1,2-f:2′,1′-d][1,3,2]dioxaphosphepin-4-amine (108 mg), and chloro(1,5-cyclooctadiene)iridium(I) dimer (27 mg) at RT under N2. The mixture was heated at reflux overnight. Evaporated material then redissoled in a 50:50 mixture of EtOH:THF. To this solution was added macro porous p-toluenesulfonic acid resin (6 g) and the mixture was gently agitated for 3 h. At this time the resin was washed completely with THF, THF:EtOH and EtOH. To a suspension of the resin in MeOH (75 ml) was added 7 N NH3.MeOH (75 ml). This mixture was gently agitated for 2 hours and filered, washing with MeOH, THF, THF:MeOH, and DCM. Evaporating this filtrate left the title compound as a yellow oil (360 mg, 89%). 1H NMR (300 MHz, CDCl3) δ 1.25-1.87 (m, 9H), 2.98-3.07 (m, 1H), 4.24 (d, 1H, J=7 Hz), 5.06-5.21 (m, 2H), 5.87-5.99 (m, 1H), 7.20-7.34 (m, 5H). MS APCI, m/z=202 (M+1), LC/MS, 1.35 min. The mixture was heated at reflux overnight At this time the resin was washed completely with THF, THF To a suspension of the resin in MeOH (75 ml) was added 7 N NH3 This mixture was gently agitated for 2 hours washing with MeOH, THF, THF Evaporating this filtrate left the title compound as a yellow oil (360 mg, 89%) MS APCI, m/z=202 (M+1), LC/MS, 1.35 min.

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of (E)-cinnamyl methyl carbonate (0.50 g) in EtOH (10 mL) at RT under N2 was added the (S)-(1,1′-Dinaphthyl-2,2′-di-(S,S)-1-phenylethylphosphoramidite (0.140 g), [Ir(COD)Cl]2 (0.035 g) and 2-methoxyethylamine (0.39 g). The reaction mixture was stirred at 50° C. for 1.5 h, then cooled to RT. The reaction mixture was diluted with ether and washed with 2N HCl (×3). The combined acidic aqueous layer was made basic with aqueous 2N NaOH and extracted with DCM (×3). The combined DCM layer was washed with brine, dried (Na2SO4), filtered and evaporated The crude material was purified via column chromatography (gradient—5%, 10%, 15% EtOAc/hexanes) to give the desired product (0.375 g, 74% ee, 75% yield). 1H NMR (300 MHz, CDCl3) δ 2.62-2.81 (m, 2H), 3.34 (s, 3H), 3.49 (t, 2H), 4.18 (d, 1H), 5.09 (d, 1H), 5.20 (dd, 1H), 5.88-5.99 (m, 1H), 7.22-7.35 (m, 5H). MS APCI, m/z=192 (M+1). LC/MS 0.66 min., Method A. cooled to RT washed with 2N HCl (×3) extracted with DCM (×3) The combined DCM layer was washed with brine dried (Na2SO4) filtered evaporated The crude material was purified via column chromatography (gradient—5%, 10%, 15% EtOAc/hexanes)

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

Procedure: To a solution of (E)-cinnamyl methyl carbonate (0.50 g) in THF (10 mL) at RT under N2 was added the (S)-(1,1′-Dinaphthyl-2,2′-di-(S,S)-1-phenylethylphosphoramidite* (0.140 g), [Ir(COD)Cl]2 (0.035 g) and benzylamine (0.557 g). The reaction mixture was stirred at reflux overnight, then cooled to RT. MP-TsOH resin (4.07 mmol/g, 2 g) was added to the reaction mixture and the resulting mixture stirred for 1 hr. The resin was then filtered from the reaction mixture and thoroughly washed with MeOH. The isolated resin was then washed separately with ammonia (7 N in MeOH) and the filtrate was concentrated to an oil. The crude material was purified via column chromatography (5% EtOAc/hexanes) to give the desired product (0.26 g, 93.5% ee, 44% yield). 1H NMR (300 MHz, CDCl3) δ 3.73 (s, 2H), 4.22 (d, 1H), 5.12 (d, 1H), 5.22 (dd, 1H), 5.89-6.01 (m, 1H), 7.21-7.38 (m, 10H). MS APCI, m/z=224 (M+1). LC/MS 1.79 min., Method A. at reflux overnight the resulting mixture stirred for 1 hr The resin was then filtered from the reaction mixture thoroughly washed with MeOH The isolated resin was then washed separately with ammonia (7 N in MeOH) the filtrate was concentrated to an oil The crude material was purified via column chromatography (5% EtOAc/hexanes)

Conditions: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of (E)-cinnamyl methyl carbonate (0.73 g) in EtOH (8 mL) at RT under N2 was added (aminomethyl)cyclopropane (1 mL), triphenyl phosphite (0.096 g) and [Ir(COD)Cl]2 (0.051 g). The reaction mixture was stirred at 85° C. overnight, then cooled to RT. MP-TsOH resin (1.3 mmol/g, 9 g) and EtOH (30 mL) were added to the reaction and the resulting mixture stirred for 2 hr. The resin was filtered from the reaction mixture and thoroughly washed with EtOH. The isolated resin was then washed separately with ammonia (7 N in MeOH) and the filtrate was concentrated to an oil. The crude material was purified via column chromatography (10% then 15% EtOAc/hexanes) to give the desired product (0.13 g, 18%). 1H NMR (300 MHz, CDCl3) δ 0.045-0.092 (m, 2H), 0.42-0.49 (m, 2H), 0.92-1.02 (m, 1H), 2.33 (dd, 1H), 2.47 (dd, 1H), 4.21 (d, 1H), 5.08 (d, 1H), 5.19 (d, 1H), 5.88-5.99 (m, 1H), 7.23(m, 5H). MS APCI, m/z=188 (M+1). LC/MS 1.25 min., Method A. cooled to RT the resulting mixture stirred for 2 hr The resin was filtered from the reaction mixture thoroughly washed with EtOH The isolated resin was then washed separately with ammonia (7 N in MeOH) the filtrate was concentrated to an oil The crude material was purified via column chromatography (10%