methyl 3-phenylprop-2-enyl carbonate

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

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

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3 (C2H5CN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D -29.7° (c 1.27, CHCl3); 99% ee. After cooling to rt were added successively The reaction mixture was heated at 65° C. for 8 h extracted with ethyl acetate The combined organic layers were dried over sodium sulfate the solvent was removed under reduced pressure The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3(EtCN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D=−29.7° (c 1.27, CHCl3); 99% ee. After cooling to rt were added successively The reaction mixture was heated at 65° C. for 8 h extracted with ethyl acetate The combined organic layers were dried over sodium sulfate the solvent was removed under reduced pressure The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3(C2H5CN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D−29.7° (c 1.27, CHCl3); 99% ee. After cooling to rt were added successively The reaction mixture was heated at 65° C. for 8 h extracted with ethyl acetate The combined organic layers were dried over sodium sulfate the solvent was removed under reduced pressure The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3 (C2H5CN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D -29.7° (c 1.27, CHCl3); 99% ee. After cooling to rt were added successively The reaction mixture was heated at 65° C. for 8 h extracted with ethyl acetate The combined organic layers were dried over sodium sulfate the solvent was removed under reduced pressure The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Cycloheptyl ligand IV (10.2 mg, 0.030 mmol) and Mo(CO)3(EtCN)3 (6.9 mg, 0.020 mmol) were dissolved in 1.0 ml of THF at rt. The reaction mixture was heated at 60° C. for 1 h. After cooling to rt, 1.0 ml of THF solution of sodium dimethylmalonate enolate, prepared from dimethyl malonate (58.0 mg, 0.44 mmol) and sodium hydride (10.2 mg, 0.40 mmol) in tetrahydrofuran, and methyl 3-phenyl-2-propenyl carbonate were added successively. The reaction mixture was heated at 65° C. for 8 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, and the solvent was removed under reduced pressure. The ratio of 1,1-dimethoxycarbonyl-2-phenyl-3-butene and linear compound was determined by 1H NMR (400 MHz) to be 34.2/1. The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield the mixture of branched and linear compound (36.7 mg, 74%). [α]D=−29.7° (c 1.27, CHCl3); 99% ee. After cooling to rt were added successively The reaction mixture was heated at 65° C. for 8 h extracted with ethyl acetate The combined organic layers were dried over sodium sulfate the solvent was removed under reduced pressure The residue was chromatographed on silica (1/8 ethyl acetate/petroleum ether, Rf=0.3) to yield

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

Procedure: By the procedure with [(COD)IrCl]2 (6.7 mg, 0.010 mmol) and L1 (Sa,Sc,Sc) (10.8 mg, 0.020 mmol) the reaction of aniline (130 mg, 1.40 mmol) and methyl cinnamyl carbonate (188 mg, 0.980 mmol) was conducted at room temperature for 24 h. 1H NMR and GC analysis of the crude reaction mixture showed that the conversion of the reaction was less than 1%. 1H NMR and GC analysis of the crude reaction mixture

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

Procedure: By the procedure for reaction of benzylamine with methyl cinnamyl carbonate, the reaction of aniline (130 mg, 1.40 mmol) and methyl cinnamyl carbonate (188 mg, 0.980 mmol) with [(COD)Ir(κ2-L1)L1] (Ir-2) (13.8 mg, 0.0100 mmol) and [(COD)IrCl]2 (3.4 mg, 0.0050 mmol) as catalyst was conducted at room temperature for 2 h. 1H NMR analysis of the crude reaction mixture indicated that the ratio of regioisomers was greater than 99/1. The mixture was then purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give 81% yield. HPLC analysis indicated that the enantiomeric excess of the product was 97% [Diacel Chiralcel® OD-H (0.46 cm×25 cm); hexanes/2-propanol=99.75/0.25; flow rate=0.6 mL/min; detection wavelength=254 nm; TR=19.1 (major) min., 20.3 min. (minor)]. [α]D20=−12.0 (c 2.10, CHCl3); 1H NMR (400.13 MHz, C6D6) δ 7.44-7.24 (m, 5H), 7.20-7.10 (m, 2H), 6.69 (t, J=7.2 Hz, 1H), 6.60 (d, J=8.0 Hz, 2H), 6.04 (ddd, J=16.8, 10.4, 6.4 Hz, 1H), 5.28 (dt, J=17.2, 1.2 Hz, 1H), 5.22 (dt, J=10.0, 1.2 Hz, 1H), 4.94 (t, J=4.4 Hz, 1H), 4.04 (br s, 1H). 13C NMR (100.5 MHz, C6D6) δ .61.1 (s, CH), 114.2 (s, CH═CH2), 115.9 (s, CH═CH2), 118.2, 127.7, 127.8, 129.1, 129.6, 139.6 (all s, Ar—CH), 142.4 (s, Ar—C), 147.8 (s, Ar—C). 1H NMR analysis of the crude reaction mixture The mixture was then purified by flash column chromatography on silica gel (1.5% ethyl acetate in hexanes) to give 81% yield

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

Procedure: A stock solution containing [(COD)IrCl]2 (3.4 mg, 0.0050 mmol) and L1 (10.8 mg, 0.0200 mmol) in 1.0 mL of THF was prepared. By the procedure for reaction of benzylamine with methyl cinnamyl carbonate, the reaction of pyrrolidine (85.0 mg, 1.19 mmol) and methyl cinnamyl carbonate (201.5 mg, 1.049 mmol) was conducted at room temperature for 16 h. 1H NMR analysis of the crude mixture showed the ratio of branched to linear product to be 99/1. After purification, 121 mg of the title compound (61%) was isolated and HPLC analysis as described above indicated that the enantiomeric excess of the major product was 97%. was prepared After purification

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

Procedure: A stock solution containing [(COD)Ir(η2-L1)(L1)] (Ir-2) (13.8 mg, 0.0100 mmol) and [(COD)IrCl]2 (3.4 mg, 0.0050 mmol) in 1.0 mL of THF was prepared. From this solution, 0.10 mL was added to 0.40 mL of THF in a screw-capped vial with a small magnetic stirbar. Pyrrolidine (87.5 mg, 1.23 mmol) and methyl cinnamyl carbonate (183 mg, 0.950 mmol) were added to the reaction mixture by syringe. The reaction was conducted at room temperature for 10 h. 1H NMR analysis of the crude mixture indicated that the ratio of the branched to linear products was 99/1. The mixture was purified by flash column chromatography on silica gel (5% ethyl acetate in hexane) to give 148 mg (81%) of the title compound. HPLC analysis indicated that the enantiomeric excess of product was 98% [Daicel Chiralcel® OD-H (0.46 cm×25 cm); hexane/diethylamine=99.75/0.25; flow rate=0.6 mL/min; detection wave length=220 nm; TR=7.60 (minor), 8.10 (major) min]; =11.2 (major), 12.5 (minor) min]: [α]DRT=+85 (c 3.2, CHCl3); 1H NMR (400.13 MHz, CDCl3) δ 7.28-7.37 (m, 4H), 7.20-7.25 (m, 1H), 6.04 (ddd, J=17.2, 10.0, 8.8 Hz,1H), 5.20 (dd, J=17.2, 1.2 Hz, 1H), 5.00 (dd, J=10.0, 1.2 Hz, 1H), 3.58 (d, J=8.8 Hz, 1H), 2.45-2.54 (m, 2H), 2.33-2.42 (m, 2H), 1.76 (m, 4H); 13C NMR (100.5 MHz, CDCl3) δ 142.7, 141.0, 128.5, 127.6, 127.1, 115.1, 75.2, 53.0, 23.3. was prepared The mixture was purified by flash column chromatography on silica gel (5% ethyl acetate in hexane)

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

Procedure: Reaction of benzylamine with methyl cinnamyl carbonate catalyzed by Complex Ir-3 and [(COE)2IrCl]2 (FIG. 2, triangles): By the procedure for reaction of the combination of Ir-2 and [(COD)IrCl]2, the reaction of benzylamine (135 mg, 1.26 mmol) and methyl cinnamyl carbonate (192 mg, 1.00 mmol) catalyzed by [(COD)Ir(κ2-L1)(PPh3)] (Ir-3) (11.0 mg, 0.0100 mmol) and [(COE)2IrCl]2 (4.4 mg, 0.0050 mmol) was monitored by GC for 10 h. 1H NMR analysis of the crude reaction showed the ratios of products to be 98/1/1, and after purification of the product by the general procedure, HPLC analysis as described above indicated that the enantiomeric excess of the major product was 97.2%. 1H NMR analysis of the crude reaction after purification of the product by the general procedure, HPLC analysis