Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: Total synthesis of ( )- pinolinone
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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Enantioselective, intermolecular [2+2] photocycloaddition reactions of 3-acetoxyquinolone: Total synthesis of ( )- pinolinone Electronic Supplementary Information (ESI) Florian Mayr, Christian Wiegand and Thorsten Bach * Lehrstuhl für Organische Chemie I, Technische Universität München, Lichtenbergstrasse 4, Garching, Germany 1. Synthetic procedures and analytical data of new compounds... S2 2. References for the Supporting Information... S32 3. NMR spectra of new compounds... S33 4. HPLC traces of racemic and enantioenriched products... S55 S1
2 1. Synthetic procedures and analytical data of new compounds General information All reactions sensitive to air or moisture were carried out in flame-dried glassware under a positive pressure of argon using standard Schlenk techniques. Dry tetrahydrofuran (THF), dichloromethane (CH 2 Cl 2 ) and diethylether (Et 2 O) were obtained from an MBRAUN MB-SPS 800 solvent purification system. Other dry solvents were obtained from Acros in the highest purity available and used without further purification. Technical solvents used for aqueous workup and for column chromatography [n-pentane (pentane), ethyl acetate (EtOAc), diethyl ether (Et 2 O), dichloromethane (CH 2 Cl 2 ), methanol (MeOH)] were distilled prior to use. Photochemical experiments were performed in Duran tubes (diameter: 1.2 cm, volume 10 ml or 20 ml each; diameter 2.0 cm, volume 60 ml) in an RPR-100 photochemical reactor (Southern New England Ultra Violet Company, Branford, CT, USA) equipped with flourescence lamps: (λ = 366 nm). Prior to irradiation, the mixture was deoxygenated by purging with argon in an ultrasonicating bath for 15 minutes before alkene were added to the mixture. Flash Chromatography was performed on silica gel 60 (Merck, mesh) with the eluent mixtures given for the corresponding procedures. Thin-layer Chromatography (TLC) was performed on silica-coated glass plates (silica gel 60 F 254). Compounds were detected by UV (λ = 254 nm, 366 nm) and CAM solution (cerium ammonium molybdate). All solvents for chromatography were distilled prior to use. Analytical HPLC was performed using a chiral stationary phase (Daicel ChiralCell, Chemical Industries, flow rate: 1.0 ml/min, type and eluent is given for the corresponding compounds) and UV detection (λ = 210 nm or 254 nm) at 20 C. IR spectra were recorded on a JASCO IR-4100 (ATR), MS and HRMS measurements were performed on a Finnigan MAT 8200 (EI). 1 H, 13 C and 31 P NMR spectra were recorded at 300 K either on a Bruker AV-250, a Bruker AV-360 or a Bruker AV-500 spectrometer. Chemical shifts are reported on parts per million (ppm) relative to residual CDCl 3 (δ H = 7.26 ppm and δ C = 77.0 ppm), DMSO-δ 6 (δ H = 2.50 ppm and δ C = 39.5 ppm). All coupling constants (J) are reported in Hertz (Hz). Apparent multiplets that occur as a result of accidental equality of coupling constants those of magnetically non-equivalent protons are S2
3 marked as virtual (virt.). Differentiable protons in cyclic systems are signed with H u = "up" and H d = "down". The relative configuration of chiral products and the multiplicity of the 13 C- NMR signals were determined by two-dimensional NMR experiments (COSY, NOESY, HSQC, HMBC). 2-Chloroquinolin-3-ol To a solution of di-iso-propylamine (4.29 ml, 3.10 g, 30.6 mmol, 1.0 equiv.) in THF (75 ml) n-butyllithium (12.2 ml, 2.5 M, 30.6 mmol, 1.0 equiv.) was added slowly at 20 C. After the addition the mixture was allowed to warm up to 0 C. After one hour at this temperature the mixture was cooled down to 78 C. 2-Chloroquinoline (5.00 g, 30.6 mmol, 1.0 equiv.) dissolved in THF (15 ml) was added dropwise. After stirring for two hours at this temperature trimethyl borate (3.40 ml, 3.21 g, 30.6 mmol, 1.0 equiv.) was added and the mixture was stirred for two hours at 78 C. Subsequently the reaction was quenched with aqueous THF (1 ml H 2 O in 6 ml THF). Water (100 ml) and Et 2 O (100 ml) were added. For the aqueous layer the ph-value was adjusted to ph = 4 by hydrochloric acid (36%). The aqueous layer was extracted with Et 2 O (3 100 ml). The combined organic layers were washed with brine, dried over sodium sulfate and filtered. The solvent was removed under reduced pressure. The residue was dissolved in Et 2 O (150 ml) and aqueous ammonium chloride (4.00 g in 160 ml H 2 O) was added. Under stirring hydrogen peroxide (40 ml, 35%) was added slowly. The mixture was stirred for four hour at room temperature. The colourless solid was collected by filtration, washed with water (150 ml) and dried under reduced pressure. The title compound (3.85 g, 21.4 mmol, 70%) was isolated as colourless solid. TLC: R f = 0.89 (EtOAc-MeOH = 9:1) [UV]. S3
4 1 H-NMR (360 MHz, DMSO-d 6 ): δ (ppm) = (m, 2 H, H-6, H-7), 7.67 (s, 1 H, H-4), (m, 2 H, H-5, H-8), (br s, 1 H, OH). 13 C-NMR (93 MHz, DMSO-d 6 ): δ (ppm) = (d, C-4), (d, C-5), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-8a), (s, C-2), (s, C-3). Analytical data are in agreement with literature data. [1] 3-Hydroxyquinolin-2(1H)-one 2-Choroquinolin-3-ol (3.85 g, 21.4 mmol, 1.0 equiv.) was suspended in aqueous hydrochloric acid (6 N, 68 ml) and stirred for 24 hours under reflux. After the reaction was complete, the mixture was cooled to room temperature and filtered. The residue was washed with water (100 ml) and dried under reduced pressure. The title compound (2.90 g, 18.0 mmol, 84%) was isolated as colourless solid. 1 H-NMR (250 MHz, DMSO-d 6 ): δ (ppm) = (m, 1 H, H-6), 7.09 (s, 1 H, H-4), (m, 2 H, H-7, H-8), (m, 1 H, H-5), 9.46 (s, 1 H, OH), (s, 1 H, NH). 13 C-NMR (63 MHz, DMSO-d 6 ): δ (ppm) = (d, C-4), (d, C-8), (s, C-4a), (d, C-6), (d, C-5), (d, C-7), (s, C-8a), (s, C-3), (s, C-2). Analytical data are in agreement with literature data. [1] S4
5 2-Oxo-1,2-dihydroquinolin-3-yl acetate (4) 3-Hydroxyquinolin-2(1H)-one (2.41 g, 14.5 mmol, 1.0 equiv.) was dissolved in dry pyridine (60 ml) and acetic anhydride (4.12 ml, 4.45 g, 45.6 mmol, 2.9 equiv.) was added. The mixture was stirred at room temperature for 24 hours. After the reaction was complete, the mixture was poured on ice water (250 ml) and filtered. The residue was recrystallised in ethanol (100 ml) and filtered. The title product 4 (2.13 g, 10.5 mmol, 72%) was isolated as colourless solid. TLC: R f = 0.23 (P/EtOAc = 1/1) [UV, CAM]. 1 H-NMR (250 MHz, DMSO-d 6 ): δ (ppm) = 2.28 (s, 3 H, OCCH 3 ), 7.22 (ddd, 3 J = 8.5 Hz, 3 J = 7.2 Hz, 4 J = 1.5 Hz, 1 H, H-6), 7.34 (dd, 3 J = 8.5 Hz, 4 J = 1.5 Hz, 1 H, H-8), 7.51 (ddd, 3 J = 8.5 Hz, 3 J = 7.2 Hz, 4 J = 1.5 Hz, 1 H, H-7), 7.66 (dd, 3 J = 8.5 Hz, 4 J = 1.5 Hz, 1 H, H-5), 7.81 (s, 1 H, H-4), 12.2 (br s, 1 H, NH). 13 C-NMR (63 MHz, DMSO): δ (ppm) = 20.3 (q, C-10), (d, C-8), (s, C-4a), (d, C-6), (d, C-5), (d, C-4), (d, C-7), (s, C-8a), (s, C-3), (s, C-2), (s, C-9). Analytical data are in agreement with literature data. [2] S5
6 [2+2] Photocycloaddition of quinolones with alkenes General procedure for racemic intermolecular [2+2] photocycloadditions: A solution of quinolone 4 in acetonitrile was purged with argon in an ultrasonicating bath for 15 minutes. The solution was divided in phototubes and the respective alkene 5a-f (20 equiv.) was added to the solution in each tube. The mixture was irradiated at room temperature at λ = 366 nm (2-3 hours). The solvent was removed under reduced pressure and the crude material was subjected to flash column chromatography using an appropriate solvent system, as described for each individual procedure. General procedure for enantioselective intermolecular [2+2] photocycloadditions: A solution of quinolone 4 (49.0 µmol) and template 6 (123 µmol, 2.5 equiv.) in toluene (10 ml) was purged with argon in an ultrasonicating bath for 15 minutes. The respective alkene 5a-f (20 equiv.) was added and the solution was transferred in a phototube. The mixture was irradiated at 70 C for 3 to 12 hours (described in each individual procedure) at λ = 366 nm. The solvent was removed under reduced pressure and the crude material was subjected to flash column chromatography using appropriate solvent system, as described for each individual procedure. S6
7 (2aS,8bS)-3-Oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinoline-1,2a(2H)-diyl diacetate (3a) Racemic procedure: Using the general procedure a mixture of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.) and vinyl acetate 5a (95.0 µl, 85.0 mg, 984 µmol, 20 equiv.) in acetonitrile (10 ml) was irradiated for three hours. Purification of the crude product by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (3:2) gave the title product 3a (13.7 mg, 47.0 µmol, 96%) as a 72:28 mixture (by 1 H-NMR spectroscopy) of two diastereomers as a colourless solid. Enantioselective procedure: Following the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.) and chiral template 6 (44.0 mg, 123 µmol, 2.5 equiv.) in toluene (10 ml) was irradiated after addition of vinyl acetate 5a (95.0 µl, 85.0 mg, 984 µmol, 20 equiv.) for three hours at 70 C. Purification of the crude product by flash column chromatography on silica ( cm) eluting with CH 2 Cl 2 -pentane-meoh (29:70:1) gave the title product 3a (10.5 mg, 36.4 µmol, 74%) as colourless solid as a 75:25 mixture of two diastereomers (by 1 H-NMR spectroscopy). m.p.: 175 C. TLC: R f = 0.42 (EtOAc-pentane = 3:2) [UV, CAM]. IR (ATR): ν (cm -1 ) = 3237 (br), 2928 (w), 1739 (m, C=O), 1681 (br, C=O), m), 1490 (m), 1371 (m), 1225 (s, C O), 1197 (s), 1077 (m), 1028 (br), 755 (m), 733 (m). S7
8 Major isomer: 1 H-NMR (500 MHz, CDCl 3 ): δ (ppm) = 1.75 (s, 3 H, H-2 ), 2.15 (s, 3 H, H-2 ), 2.80 (dd, 2 J = 14.3 Hz, 3 J = 5.6 Hz, 1 H, H-2 u ), 3.09 (ddd, 2 J = 14.3 Hz, 3 J = 8.1 Hz, 4 J = 3.3 Hz, 1 H, H- 2 d ), 4.10 (dd, 3 J = 7.8 Hz, 4 J = 3.3 Hz, 1 H, H-8b), 5.57 (virt. td, 3 J = 7.8 Hz, 3 J = 5.6 Hz 1 H, H-1), 6.77 (dd, 3 J = 7.5 Hz, 4 J = 1.1 Hz, 1 H, H-5), 6.91 (d, 3 J = 7.5 Hz, 1 H, H-8), 6.98 (td, 3 J = 7.5 Hz, 4 J = 1.1 Hz, 1 H, H-7), 7.19 (td, 3 J = 7.5 Hz, 4 J = 1.1 Hz, 1 H, H-6), 8.26 (s, 1 H, H-4). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 20.6 (q, C-2 ), 21.0 (q, C-2 ), 38.8 (t, C-2), 50.2 (d, C-8b), 66.7 (d, C-1), 72.6 (s, C-2a), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C-1 ), (s, C-1 ). Minor isomer: 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 20.6 (1, C-2 ), 21.0 (q, C-2 ), 40.4 (t, C-2), 53.3 (d, C-8b), 68.6 (d, C-1), 69.9 (s, C-2a), (d, C-5), (s, C-8a), (d, C-7), (d, C-8), (d, C-6), (s, C-4a), (s, C-3), (s, C-1 ), (s, C-1 ). S8
9 MS (EI, 70 ev) m/z (%) = 289 (5) [M + ], 230 (10) [(C 13 H 12 NO 3 ) + ], 188 (80) [(C 11 H 9 NO 2 ) + ], 161 (100) [(C 9 H 6 NO 2 ) + ], 159 (40), 149 (25), 84 (35), 57 (33), 43 (82). HRMS (EI): C 15 H 15 NO 5 calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 28.4 min, 32.2 min, 39.2 min, 44.5 min; t R [ent-3a] = 31.7 min, 38.6 min, t R [3a] = 28.2 min, 44.0 min; 87% ee, 89% ee (AD-H mm, n- hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = (c = 0.53, MeOH). (2aS,8bR)-1,1-Dichloro-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate (3b) Racemic procedure: Using the general procedure a mixture of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.) and 1,1-dichloroethene 5b (80.0 µl, 94.0 mg, 984 µmol, 20 equiv.) in acetonitrile (10 ml) gave the crude product. Purification of the crude product by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (2:3) gave the title compound 3b (14.5 mg, 49.0 µmol, quant.) as colourless solid. Enantioselective procedure: Following the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.), template 6 (44.0 mg, 123, µmol, 2.5 equiv.) and 1,1-dichloroethene 5b (80.0 µl, 94.0 mg, 984 µmol, 20 equiv.) in toluene (10 ml) was irradiated for three hours at 74 C. Purification of the crude product by flash column chromatography on silica ( cm) eluting with S9
10 EtOAc-pentane (2:3) gave the title compound 3b (14.8 mg, 49.0 µmol, quant.) as colourless solid. m.p.: 178 C. TLC: R f = 0.70 (EtOAc-pentane = 3:2) [UV, CAM]. IR (ATR): ν (cm -1 ) = 3368 (w), 2957 (w), 1749 (m, C=O), 1684 (s, C=O), 1483 (m), 1366 (br), 1235 (s, C O), 1069 (m), 1007 (m), 764 (s). 1 H-NMR (500 MHz. CDCl 3 ): δ (ppm) = 2.13 (s, 3 H, H-2 ), 3.68 (d, 2 J = 15.2 Hz, 1 H, H-2 u ), 3.72 (dd, 2 J = 15.2 Hz, 4 J = 1.6 Hz, 1 H, H-2 d ), 4.49 (s, 1 H, H-8b), 6.85 (dd, 3 J = 7.5 Hz, 4 J = 1.3 Hz, 1 H, H-5), 7.10 (td, 3 J = 7.5 Hz, 4 J = 1.3 Hz, 1 H, H-7), 7.16 (dd, 3 J = 7.5 Hz, 4 J = 1.5 Hz, 1 H, H-8), 7.29 (td, 3 J = 7.5 Hz, 4 J = 1.5 Hz. 1 H, H-6), 8.79 (s, 1 H, H-4). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 20.5 (q, C-2 ), 56.5 (t, C-2), 64.7 (d, C-8b), 69.6 (s, C-2a), 80.3 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-8), (d, C-6), (s, C-4a), (s, C-3), (s, C-1). MS (EI, 70 ev) m/z (%) = 299 (2) [M + ], 203 (7) [(C 11 H 9 NO 3 ) + ], 195 (4), 162 (10), 161 (100) [(C 9 H 6 NO 2 ) + ], 124 (15), 109 (15), 86 (20), 84 (33). HRMS (EI): C 13 H 11 NO 3 Cl 2 : calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 35.5 min, 38.0 min; t R [3b] = 37.7 min, t R [ent-3b] = 40.0 min, 57% ee (AD-H, mm, n-hexane/i-proh = 95:5, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = (c = 0.69, MeOH) S10
11 (2aS,8bR)-1,1-Diethyl-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl (3c) acetate Racemic procedure: Using the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.) in acetonitrile (10 ml) with 2-ethyl-1-butene 5c (120 µl, 83.0 mg, 984 µmol, 20 equiv.) gave the crude product. Purification by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (2:3) gave the title product 3c (8.70 mg, 30.0 µmol, 62%) as colourless solid. Enantioselective procedure: Following the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.), template 6 (44.0 mg, 123 µmol, 2.5 equiv.) and 2-ethyl-1-butene 5c (120 µl, 83.0 mg, 984 µmol, 20 equiv.) in toluene (10 ml) gave the crude product. Purification by flash column chromatography ( cm) eluting with CH 2 Cl 2 -pentane-meoh (29:70:1) and a second flash column chromatography ( cm) eluting with EtOAc-pentane (1:1) gave the title product 3c (4.00 mg, 14.0 µmol, 29%) as colourless solid. m.p.: 148 C. S11
12 TLC: R f = 0.50 (EtOAc-pentane = 1:1) [UV, CAM]. IR (ATR): ν (cm -1 ) = 2967 (w), 2924 (w), 1746 (m, C=O), 1682 (s, C=O), 1593 (w), 1493 (m), 1391 (m), 1366 (m), 1229 (s, C O), 1088 (m), 1022 (m), 755 (s). 1 H-NMR (500 MHz CDCl 3 ): δ (ppm) = 0.61 (t, 3 J = 7.6 Hz, 3 H, H-2 ), 0.93 (t, 3 J = 7.3 Hz, 3 H, H-2 ), 1.03 (dq, 2 J = 15.0 Hz, 3 J = 7.6 Hz, 1 H, H-1 ), 1.12 (dq, 2 J = 15.0 Hz, 3 J = 7.8 Hz, 1 H, H-1 ), (m, 2 H, H-1 ), 2.10 (s, 3 H, H-2 ), 2.38 (d, 2 J = 14.0 Hz, 1 H, H-2 u ), 2.50 (dd, 2 J = 14.0 Hz, 4 J = 1.2 Hz, 1 H, H-2 d ), 3.47 (s, 1 H, H-8b), 6.47 (d, 3 J = 7.6 Hz, 1 H, H-5), (m, 2 H, H-7, H-8), 7.14 (td, 3 J = 7.6 Hz, 4 J = 2.2 Hz, 1 H, H-6), 8.14 (s, 1 H, H-4). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 7.3 (q, C-2 ), 8.2 (q, C-2 ), 20.8 (q, C-2 ), 25.5 (t, C-1 ), 32.4 (t, C-1 ), 40.4 (s, C-1), 42.5 (t, C-2), 53.2 (d, C-8b), 71.7 (s, C-2a), (d, C- 5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C- 3), (s, C-1 ). MS (EI, 70 ev) m/z (%) = 287 (1) [M + ], 228 (5), 203 (6) [(C 11 H 9 NO 3 ) + ], 195 (6), 162 (8), 161 (100) [(C 9 H 6 NO 2 ) + ], 152 (6), 86 (15), 84 (25), 49 (17). HRMS (EI): C 17 H 21 NO 3 : calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 16.4 min, 21.1 min; t R [3c] = 16.9 min, t R [ent-3c] = 21.8 min, 79% ee (AD-H, mm, n-hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = (c = 0.21, MeOH). S12
13 (2aR,8bR)-1,1,2,2-Tetramethyl-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate (3d) Racemic procedure: Using the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.) and 2,3-dimethyl-2-butene 5d (100 µl, 83.0 mg, 984 µmol, 20 equiv.) in acetonitrile (10 ml) was irradiated for three hours. Purification of the crude product by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (2:3) gave the title product 3d (14.5 mg, 49.0 µmol, quant.) as colourless solid. Enantioselective procedure: Following the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.), template 6 (44.0 mg, 123 µmol, 2.5 equiv.) and 2,3-dimethyl-2-butene 5d (100 µl, 83.0 mg, 984 µmol, 20 equiv.) in toluene (10 ml) was irradiated for three hours. Purification of the crude product by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (2:3) gave the title product 3d (14.2 mg, 49.0 µmol, quant.) as colourless solid. S13
14 m.p.: 182 C. TLC: R f = 0.65 (EtOAc-pentane = 1:1) [UV, CAM]. IR (ATR): ν (cm -1 ) = 2991 (w), 1738 (m, C=O), 1677 (s, C=O), 1595 (m), 1495 (m), 1366 (br), 1242 (br, C O), 1118 (m), 1037 (m), 746 (s). 1 H-NMR (500 MHz, CDCl 3 ): δ (ppm) = 0.68 (s, 3 H, H-1 ), 1.09 (s, 3 H, H-2 ), 1.22 (s, 3 H, H-1 ), 1.31 (s, 3 H, H-2 ), 2.08 (s, 3 H, H-2 ), 3.36 (s, 1 H, H-8b), 6.70 (dd, 3 J = 7.5 Hz, 4 J = 1.2 Hz, 1 H, H-5), 6.90 (dd, 3 J = 7.5 Hz, 4 J = 1.5 Hz, 1 H, H-8), 6.98 (td, 3 J = 7.5 Hz, 4 J = 1.2 Hz, 1 H, H-7), 7.15 (td, 3 J = 7.5 Hz, 4 J = 1.5 Hz. 1 H, H-6), 7.76 (s, 1 H, H-4). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 20.9 (q, C-1 ), 20.9 (q, C-2 ), 21.4 (q, C-2 ), 21.6 (q, C-2 ), 26.6 (q, C-1 ), 41.2 (s, C-1), 46.6 (s, C-2), 53.0 (d, C-8b), 78.2 (s, C-2a), (d, C-5), (s, C-8a), (d, C-7), (s, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C1). MS (EI, 70 ev) m/z (%) = 287 (7) [M + ], 227 (7) [(M-C 2 H 4 O 2 ) + ], 212 (8), 204 (25), 162 (30), 161 (100) [(C 9 H 6 NO 2 ) + ], 86 (23), 84 (35). HRMS (EI): C 17 H 21 NO 3 : calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 12.6 min, 15.7 min; t R [3d] = 13.1 min, t R [ent-3d] = 16.4 min; 55% ee (AD-H, mm, n-hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = 84.2 (c = 0.60, MeOH). S14
15 (2aS,8bR)-1,1-Diethoxy-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate (3e) Racemic procedure: Using the general procedure a solution of quinolone 4 (120 mg, 591 µmol, 1.0 equiv.) and 1,1-diethoxyethene 5e (1.56 ml, 1.37 g, 11.8 mmol, 20 equiv.) in acetonitrile (120 ml) was irradiated for two hours. Purification of the crude product by flash column chromatography on silica ( 25 3 cm) eluting with EtOAc-pentane (3:2) gave the title product 3e (133 mg, 416 µmol, 70%) as colourless solid. Enantioselective procedure: Following the general procedure a solution of quinolone 4 (10.0 mg, 49.0 µmol, 1.0 equiv.), template 6 (44.0 mg, 123 µmol, 2.5 equiv.) and 1,1-diethoxyethene 5e (130 µl, 114 mg, 984 µmol, 20 equiv.) in toluene (10 ml) was irradiated for three hours. Purification of the crude product by flash column chromatography on silica ( cm) eluting with EtOAc-pentane (3:7 1:1) gave the title compound 3e (10.5 mg, 33.0 µmol, 67%) as colourless solid. The mixture of template 6 and quinolone 4 can be separated by a second flash column chromatography on silica ( 20 3 cm) eluting with CH 2 Cl 2 -pentane-meoh (29:70:1). S15
16 m.p.: 194 C. TLC: R f = 0.41 (EtOAc-pentane = 1:1) [UV, CAM]. IR (ATR): ν (cm -1 ) = 3194 (w), 3059 (w, NH), 2925 (w), 1747 (s, C=O), 1681 (br, C=O), 1595 (m), 1496 (m), 1401 (m), 1263 (m, C O), 1237 (s), 1090 (m), 1063 (s), 1041 (s), 765 (s). 1 H-NMR (250 MHz, CDCl 3 ): δ (ppm) = 0.88 (t, 3 J = 7.5 Hz, 3 H, H-2 ), 1.24 (t, 3 J = 7.5 Hz, 3 H, H-2 ), 2.08 (s, 3 H, H-2 ), 2.81 (dd, 2 J = 13.7 Hz, 4 J = 1.5 Hz, 1 H, H-2 d ), 2.84 (d, 2 J = 13.7 Hz, 1 H, H-2 u ), (m, 1 H, H-1 ), (m, 1 H, H-1 ), (m, 1 H, H-1 ), (m, 1 H, H-1 ), 3.85 (s, 1 H, H-8b), 6.75 (d, 3 J = 7.5 Hz, 1 H, H-5), 6.98 (t, 3 J = 7.5 Hz, 1 H, H-7), 7.08 (d, 3 J = 7.5 Hz, 1 H, H-8), 7.17 (td, 3 J = 7.5 Hz, 4 J = 1.6 Hz 1 H, H-6), 8.30 (s, 1 H, H-4). 13 C-NMR (63 MHz, CDCl 3 ): δ (ppm) = 15.1 (q, C-2 ), 15.2 (q, C-2 ), 20.6 (q, C-2 ), 44.2 (t, C-2), 56.8 (d, C-8b), 57.2 (t, C-1 ), 57.7 (t, C-1 ), 69.0 (s, C-2a), 97.4 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C-1 ). MS (EI, 70 ev): m/z (%) = 319 (1) [M + ], 260 (40) [(C 15 H 18 NO 3 ) + ], 232 (10), 186 (65) [(C 11 H 8 NO 2 ) + ], 161 (20), 159 (25), 158 (100), 130 (15), 116 (15), 89 (15), 84 (20). HRMS (EI) C 17 H 21 NO 5 : calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 8.56 min, 28.2 min; t R [ent-3e] = 8.91 min, t R [3e] = 27.9 min; 95% ee (AS-H, mm, n-hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = 155 (c = 0.53, MeOH). S16
17 (2aS,8bR)-1-((tert-Butyldimethylsilyl)oxy)-1-methoxy-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate (3f) Racemic procedure: Using the general procedure a solution of quinolone 4 (170 mg, 837 µmol, 1.0 equiv.) and tert-butyl-[(1-methoxyvinyl)oxy]-dimethylsilane 5f (3.40 ml, 16.7 mmol, 20 equiv.) in acetonitrile (170 ml) was irradiated for three hours. Before purification the residual olefin should be decomposed by addition of MeOH. Purification of the crude product by flash column chromatography on silica ( 25 4 cm) eluting with EtOAc-pentane (1:4) gave the title compound 3f (193 mg, 492 µmol, 59%) as colourless solid in a diastereomeric mixture 62:38 (by 1 H-NMR spectroscopy). Enantioselective procedure: Following the general procedure a solution of quinolone 4 (50.0 mg, 246 µmol, 1.0 equiv.), template 6 (217 mg, 615 µmol, 2.5 equiv.) and tert-butyl-[(1-methoxyvinyl)oxy]- dimethylsilane 5f (1.00 ml, 492 mmol, 20 equiv.) in toluene (50 ml) was irradiated for twelve hours at 70 C. Before purification the residual olefin should be decomposed with MeOH. Purification of the crude product by flash column chromatography on silica ( 20 2 cm) eluting with EtOAc-pentane (2:3) gave the title compound 3f (93.5 mg, 239 µmol, 97%) as colourless solid in a diastereomeric mixture 71:29 (by 1 H-NMR spectroscopy). m.p.: 98 C. TLC: R f = 0.59 (EtOAc-pentane = 1:1) [UV, CAM]. S17
18 IR (ATR): ν =3214 (w, NH), 2956 (m), 2928 (m, CH), 1742 (m, C=O), 1671 (s), 1595 (w), 1492 (w), 1372 (w), 1241 (m, C O), 1197 (w), 1132 (w), 1122 (w), 1093 (w), 1071 (m), 838 (m), 754 (m). Major isomer: 1 H-NMR (360 MHz, CDCl 3 ): δ (ppm) = 0.18 [s, 3 H, Si(CH 3 )(CH 3 )], 0.20 [s, 3 H, Si(CH 3 )(CH 3 )], 0.95 [s, 9 H, SiC(CH 3 ) 3 ], 2.09 (s, 3 H, H-2 ), 2.87 (dd, 2 J = 13.5 Hz, 4 J = 2.2 Hz, 1 H, H-2 d ), 2.93 (s, 3 H, OCH 3 ) 3.06 (d, 2 J = 13.5 Hz, 1 H, H-2 u ), 3.82 (s, 1 H, H-8b), 6.73 (d, 3 J = 8.1 Hz, 1 H, H-5), (m, 1 H, H-7), 7.11 (d, 3 J = 7.7 Hz, 1 H, H-8), (m, 1 H, H-6), 7.80 (br s, 1 H, NH). 13 C-NMR (63 MHz, CDCl 3 ): δ (ppm) = 3.2 [q, Si(CH 3 )(CH 3 )], 2.9 [q, Si(CH 3 )(CH 3 )], 18.2 [s, SiC(CH 3 ) 3 ], 20.7 (q, C-2 ), 25.8 [q, SiC(CH 3 ) 2 ], 47.6 (t, C-2), 50.2 (q, OCH 3 ), 59.8 (d, C-8b), 68.9 (s, C-2a), 96.3 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C-1 ). Minor isomer: S18
19 13 C-NMR (63 MHz, CDCl 3 ): δ (ppm) = 3.6 [q, Si(CH 3 )(CH 3 )], 3.4 [q, Si(CH 3 )(CH 3 )], 17.8 [s, SiC(CH 3 ) 3 ], 20.7 (q, C-2 ), 25.3 [q, SiC(CH 3 ) 3 ], 48.6 (t, C-2), 49.7 (q, OCH 3 ), 56.7 (d, C-8b), 69.0 (s, C-2a), 96.4 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C-1 ). MS (EI, 70 ev): m/z (%) = 332 (100) [(M-OAc) + ], 274 (30) [(C 14 H 12 NO 5 ) + ], 216 (30), 185 (81), 158 (59) [(C 9 H 4 NO 2 ) + ], 129 (43), 89 (73), 75 (75), 43 (97) [(C 2 H 3 O) + ]. HRMS (EI): C 18 H 26 NO 3 Si calc.: [(M-OAc) + ]: found: [(M-OAc) + ]: Chiral HPLC: t R [racemate] = 10.1 min, 12.1 min, 16.8 min, 22.4 min; t R [3f] = 10.1 min, 16.9 min, t R [ent-3f] = 12.1 min, 22.5 min; 88% ee, 95% ee, (AD-H, mm, n- hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm, 254 nm). Specific rotation: [α] 20 D = 136 (c = 0.48, CH 2 Cl 2 ). For product 3f different conditions were tested (chart 1). chart 1: Dependence of temperature and solvent for yield, diastereomeric ratio and enantiomeric excess. entry solvent temp [ C] yield [%] d.r. ee 1 a tol r.t :38 26%, 27% 2 a tol :31 88%, 89% 3 b tol :29 88%, 95% 4 a PhCF :30 56%, 60% 5 a MeCN :34 0%, 0% 6 a THF :43 2%, 6% 7 a EtOAc :42 17%, 18% 8 a MeOH :33 6%, 3% a: reaction was performed for three hours at λ = 366 nm; b: reaction was performed for twelve hours at λ = 366 nm. S19
20 (2aS,8bR)-1-((tert-Butyldimethylsilyl)oxy)-1-methoxy-4-methyl-3-oxo-1,3,4,8b-tetrahydrocyclobuta[c]quinolin-2a(2H)-yl acetate (9) Racemic procedure: Photoproduct 3f (555 mg, 1.42 mmol, 1.0 equiv.) was dissolved in THF (20 ml) and cooled to 0 C. At this temperature sodium hydride (62.3 mg, 60%, 1.55 mmol, 1.1 equiv.) was added and the mixture was allowed to stir for 30 minutes. After that period of time methyl iodide (0.44 ml, 1.02 g, 7.08 mmol, 5.0 equiv.) was added dropwise. The mixture was allowed to warm up to room temperature over night. The solvent was removed under reduced pressure. Purification by flash column chromatography on silica ( 30 4 cm) eluting with EtOAc-pentane (1:9 1:1) gave the title compound 9 (425 mg, 1.05 mmol, 74%) as colourless oil in a diastereomeric mixture 62:38 (by 1 H-NMR spectroscopy). Enantioselective procedure: In analogue way photoproduct 3f of enantioselective photoreaction was realized in a scale of 761 µmol. So quinolone 9 (167 mg, 412 µmol, 54%) was isolated as colourless oil in a diastereomeric mixture 74:26 (by 1 H-NMR spectroscopy). TLC: R f = 0.69 (EtOAc-pentane = 3:2) [UV, CAM]. IR (ATR): ν = 2953 (m, C-H), 2854 (w, C-H), 1735 (s, C=O), 1644 (br, C=O), 1599 (m), 1472 (m), 1372 (w), 1230 (br, C O), 759 (m). S20
21 Major isomer: 1 H-NMR (250 MHz, CDCl 3 ): δ (ppm) = 0.17 [s, 3 H, Si(CH 3 )(CH 3 )], 0.18 [s, 3 H, Si(CH 3 )(CH 3 )], 0.95 [s, 9H, Si(CH 3 ) 3 ], 2.05 (s, 3 H, H-2 ), 2.88 (s, 3 H, OCH 3 ), 2.89 (d, 2 J = 2.1 Hz, 1 H, H-2 u ), 3.02 (d, 4 J = 13.7 Hz, 1 H, H-2 d ), 3.40 (s, 3 H, NCH 3 ), 3.78 (s, 1 H, H-8b), (m, 1 H, H-5), (m, 1 H, H-7), 7.11 (dd, 3 J = 7.4 Hz, 4 J = 1.7 Hz, 1 H, H-8), (m, 1 H, H-6). 13 C-NMR (63 MHz, CDCl 3 ): δ (ppm) = 3.2 [q, Si(CH 3 )(CH 3 )], 3.0 [q, C-Si(CH 3 )(CH 3 )], 18.2 [s, SiC(CH 3 ) 3 ], 20.7 (q, C-2 ), 25.8 [q, SiC(CH 3 ) 3 ], 30.1 (q, NCH 3 ), 48.2 (t, C-2), 50.3 (q, OCH 3 ), 59.1 (d, C-8b), 68.6 (s, C-2a), 96.0 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3), (s, C-1 ). Minor isomer: O OTBS u H H 1 d H 7 8b 1 O 3 O 4a N O 13 C-NMR (63 MHz, CDCl 3 ): δ (ppm) = 3.6 [q, Si(CH 3 )(CH 3 )], 3.5 [q, Si(CH 3 )(CH 3 )], 17.8 [s, SiC(CH 3 ) 3 ], 20.7 (q, C-2 ), 25.3 [q, SiC(CH 3 ) 3 ], 30.0 (q, NCH 3 ), 49.1 (t, C-2), 49.8 (q, OCH 3 ), 56.1 (d, C-8b), 68.5 (s, C-2a), 96.0 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d,c-8), (s, C-4a), (s, C-3), (s, C-1 ). S21
22 MS (EI, 70 ev): m/z (%) = 346 (100) [(M-C 2 H 3 O 2 ) + ], 231 (57), 216 (52) [(C 12 H 10 NO 3 ) 3+ ], 200 (66) [(C 12 H 10 NO 2 ) 2+ ], 199 (77), 175 (54), 172 (96), 89 (44), 75 (66), 73 (36), 57 (20), 44 (36). HRMS (EI): C 19 H 28 O 3 NSi calc.: [(M-OAc) + ]: found: [(M-OAc) + ]: Specific rotation: [α] 20 D = 146 (c = 0.64, CH 2 Cl 2 ). (2aS,8bR)-1-((tert-Butyldimethylsilyl)oxy)-2a-hydroxy-1-methoxy-4-methyl-2,2a,4,8btetrahydrocyclobuta[c]quinolin-3(1H)-one (10) Racemic procedure: Quinolone 9 (458 mg, 1.13 mmol 1.0 equiv.) was dissolved in ethanol (38 ml) and potassium cyanide (36.7 mg, 569 µmol, 0.5 equiv.) was added. The mixture was stirred for six hours at 80 C. The solvent was removed under reduced pressure. Purification of the crude product by flash column chromatography on silica ( 25 3 cm) eluting with EtOAc-pentane (1:9 1:4) gave the title compound 10 (398 mg, 1.10 mmol, 97%) as colourless oil in a diastereomeric mixture 67:33 (by 1 H-NMR spectroscopy). Enantioselective procedure: In analogue way quinolone 9 was used as starting material in a scale of 354 µmol. On that way quinolone 10 (129 mg, 354 µmol, quant.) was isolated as colourless oil in a diastereomeric mixture 70:30 (by 1 H-NMR spectroscopy). S22
23 TLC: R f = 0.63 (pentane-etoac = 1:1) [UV, CAM]. IR (ATR): ν = 3372 (b, OH), 2926 (m, C-H), 1791 (m, C=O), 1733 (m), 1637 (s, C=O), 1597 (s), 1466 (m), 1383 (w), 1273 (w), 1247 (w, C O), 1222 (w), 1207 (w), 754 (m). Major isomer: 1 H-NMR (500 MHz, CDCl 3 ): δ (ppm) = 0.18 [s, 6 H, Si(CH 3 ) 2 ] 0.95 [s, 9 H, SiC(CH 3 ) 3 ], 2.58 (dd, 2 J = 12.5 Hz, 4 J = 1.6 Hz, 1 H, H-2 d ), 2.88 (s, 3 H, NCH 3 ), 3.02 (d, 2 J = 12.5 Hz, 1 H, H-2 u ), 3.40 (s, 3 H, OCH 3 ), 3.82 (s, 1 H, H-8b), (m, 1 H, H-5), (m, 1 H, H-7), 7.19 (dd, 3 J = 7.5 Hz, 4 J = 1.7 Hz, 1 H, H-8), (m, 1 H, H-6). 13 C-NMR (126 MHz, CDCl 3 ): δ (ppm) = 3.1 [q, Si(CH 3 )(CH 3 )], 3.0 [q, Si(CH 3 ) (CH 3 )], 18.2 [s, SiC(CH 3 ) 3 ], 25.8 [q, SiC(CH 3 ) 3 ], 29.9 (q, NCH 3 ), 50.4 (q, OCH 3 ), 50.6 (t, C-2), 57.6 (d, C-8b), 65.4 (s, C-2a), 95.5 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3). Minor isomer: 7 8b 3 4a O OTBS u H H 1 H OH N O d 13 C-NMR (126 MHz, CDCl 3 ): δ (ppm) = 3.7 [q, Si(CH 3 )(CH 3 )], 3.5 [q, Si(CH 3 )(CH 3 )], 17.8 [s, SiC(CH 3 ) 3 ], 25.4 [q, SiC(CH 3 ) 3 ], 29.9 (q, NCH 3 ), 50.0 (q, OCH 3 ), 52.4 (t, C-2), 54.3 S23
24 (d, C-8b), 65.2 (s, C-2a), 96.4 (s, C-1), (d, C-5), (s, C-8a), (d, C-7), (d, C-6), (d, C-8), (s, C-4a), (s, C-3). MS (EI, 70 ev): m/z (%) = 232 (9) [(M-OTBDMS) + ], 231 (19), 216 (23) [(C 13 H 13 NO 2 ) + ], 175 (100) [(C 10 H 9 NO 2 ) 2+ ], 172 (13), 147 (26), 118 (9), 89 (6), 77 (6). HRMS (EI): C 13 H 13 NO 3 calc.: [(M-C 6 H 16 OSi) + ]: found: [(M-C 6 H 16 OSi) + ]: Chiral HPLC: t R [racemate] = 9.14 min, 10.1 min, 22.0 min, 39.9 min; t R [ent-10] = 9.07 min, 39.8 min, t R [10] = 9.88 min, 21.6 min; 93% ee, 85% ee (AD-H, mm, n- hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = 121 (c = 0.86, CH 2 Cl 2 ). (3aS,9bR)-3a-Hydroxy-5-methyl-3,3a,5,9b-tetrahydrofuro[3,2-c]quinoline-2,4-dione (2) Racemic procedure: Quinolone 10 (80.0 mg, 0.22 mmol, 1.0 equiv.) was dissolved in CH 2 Cl 2 (6 ml) and cooled down to 0 C. At this temperature boron trifluoride diethyl etherate (27.8 µl, 31.2 mg, 0.22 mmol, 1.0 equiv.) was added dropwise. The mixture was stirred for 30 minutes and afterwards meta-chloroperoxybencoic acid (59.7 mg, 70%, 0.24 mmol, 1.1 equiv.) was added. The mixture was allowed to warm up to room temperature over night. The solvent was removed under reduced pressure and purification by flash column chromatography on silica S24
25 ( 20 3 cm) eluting with EtOAc-pentane (3:7) gave the title product 2 (38.9 mg, 0.17 mmol, 76%) as colourless solid. Enantioselective procedure: In analogue way quinolone 10 was used as starting material in a scale of 0.22 mmol. Lactone 2 (58.2 mg, 250 µmol, 75%) was isolated as colourless solid. At this step the product was purified by semipreparative HPLC (n-hexane/i-proh = 50:50, 15 ml/min, 70 min, λ = 215 nm) to get a clean product with an enantiomeric excess of 99% ee. m.p.: 191 C. TLC: R f = 0.28 (pentane-etoac = 1:1) [UV, CAM]. IR (ATR): ν = 3351 (b, OH), 3075 (w), 2925 (w, C-H), 1785 (s, C=O), 1644 (s, C=O), 1600 (s), 1469 (m), 1382 (m), 1167 (m, C O), 1085 (m), 1001 (m), 761 (m). 1 H-NMR (360 MHz, CDCl 3 ): δ (ppm) = 2.68 (dd, 2 J = 17.2 Hz, 4 J = 1.2 Hz, 1 H, H-3 d ), 2.76 (d, 2 J = 17.2 Hz, 1 H, H-3 u ), 3.47 (s, 3 H, NCH 3 ), 4.26 (s, 1 H, OH), 5.69 (d, 4 J = 1.2 Hz, 1 H, H-9b), 7.07 (d, 3 J = 7.5 Hz, 1 H, H-6), (m, 1 H, H-8), 7.43 (td, 3 J = 7.5 Hz, 4 J = 0.7 Hz, 1 H, H-7), 7.54 (d, 3 J = 7.5 Hz, 1 H, H-9). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 30.5 (q, NCH 3 ), 41.5 (t, C-3), 74.9 (s, C-3a), 82.3 (d, C-9b), (d, C-6), (s, C-9a), (d, C-8), (d, C-9), (d, C-7), (s, C-5a), (s, C-4), (s, C-2). MS (EI, 70eV): m/z (%) = 233 (25) [M + ], 215 (9), 187 (6) [(C 11 H 9 NO 2 ) + ], 160 (8), 146 (12) [(C 9 H 8 NO) 2+ ], 70 (11), 61 (14), 45 (12), 43 (100) [(CO 2 ) 2+ ]. S25
26 HRMS (EI): C 12 H 11 NO 4 calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 6.90 min, 9.60 min; t R [ent-2] = 9.60 min, t R [2] = 6.91 min, 87% ee (AD-H, mm, n-hexane/i-proh = 50:50, 1mL/min, λ = 210 nm). Specific rotation: [α] 20 D = 137 (c = 0.36, CH 2 Cl 2 ). (3aS,9bR)-2,3a-Dihydroxy-5-methyl-3,3a,5,9b-tetrahydrofuro[3,2-c]quinolin-4(2H)-one (11) Racemic procedure: Lactone 2 (40.0 mg, 172 µmol, 1.0 equiv.) was dissolved in CH 2 Cl 2 (6 ml) and cooled down to 78 C. At this temperature di-iso-butylaluminium hydride (257 µl, 1 M in CH 2 Cl 2, 257 µmol, 1.5 equiv.) was added dropwise. The mixture was stirred for one hour and afterwards di-iso-butylaluminium hydride (257 µl, 1 M in CH 2 Cl 2, 257 µmol, 1.5 equiv.) was added again. After a further hour MeOH (4 ml) was added and the mixture was warmed to room temperature. At room temperature saturated sodium-potassium-tartrate solution (6 ml) was added and the mixture was stirred for one hour. Finally saturated sodium chloride solution (6 ml) was added. The mixture was extracted with CH 2 Cl 2 (4 10 ml). The combined organic phases were dried over sodium sulfate and filtered. The solvent was removed under reduced pressure. Purification by flash column chromatography on silica ( cm) with a dryload on celite eluting with EtOAc-pentane (3:7 1:1) gave the title compound 11 (24.6 mg, 105 µmol, 61%) as colourless oil. S26
27 Enantioselectiv procedure: In analogue way lactone 2 was used as starting material in a scale of 126 µmol. Lactole 11 (17.9 mg, 75.9 µmol, 60%) was isolated as colourless oil. TLC: R f = 0.14 (P/EtOAc = 1/1) [UV, CAM]. IR (ATR): ν = 3392 (b, OH), 2928 (m, C-H), 1662 (s, C=O), 1604 (s), 1475 (m), 1129 (w). 1 H-NMR (360 MHz, CDCl 3 ): δ (ppm) = (m, 2H, H-3), 3.44 (s, 3H, H-NCH 3 ), 4.12 (brs, 1H, H-=H), 4.46 (brs, 1H, H-OH), (m, 2H, H-2, H-9b), 6.99 (dd, 3 J = 7.7 Hz, 4 J = 1.2 Hz, 1H, H-6), 7.17 (td, 3 J = 7.7 Hz, 4 J = 1.2 Hz, 1H, H-8), 7.34 (td, 3 J = 7.7 Hz, 4 J = 1.5 Hz, 1H. H-7), 7.56 (dd, 3 J = 7.7 Hz, 4 J = 1.5 Hz, 1H, H-9). 13 C-NMR (91 MHz, CDCl 3 ): δ (ppm) = 30.3 (q, NCH 3 ), 45.6 (t, C-3), 77.8 (d, C-9b), 81.2 (s, C-3a), 98.4 (d, C-2), (d, C-6), (s, C-9a), (d, C-8), (d, C-9), (d, C-7), (s, C-5a), (s, C-4). MS (EI,70 ev): m/z (%) = 235 (6) [M + ], 146 (6) [(C 9 H 8 NO) 2+ ], 100 (13), 84 (95), 82 (26), 66 (100), 48 (13), 46 (20). HRMS (EI): C 12 H 13 NO 4 calc.: [M + ]: found: [M + ]: S27
28 (3S,4R)-3,4-Dihydroxy-1-methyl-3-(3-methylbut-2-en-1-yl)-3,4-dihydroquinolin-2(1H)- one (1) Racemic procedure: In a first step triphenyl-iso-propylphosphoniumbromide (167 mg, 434 µmol, 10 equiv.) was suspended in THF (4 ml) and n-butyllithium (0.17 ml, 2.5 M in hexane, 434 µmol, 10 equiv.) was added slowly and the mixture was stirred for 30 minutes. To that mixture lactole 11 (10.2 mg, 43.4 µmol, 1.0 equiv.) dissolved in THF (4 ml) was added dropwise at 0 C. The mixture was stirred for three hours and finally quenched by addition of EtOAc (4 ml). The crude product was purified by flash column chromatography on silica ( cm) with a dryload on celite eluting with EtOAc-pentane (1:2). So natural product 1 (5.67 mg, 21.7 µmol, 50%) was isolated as colourless oil. In analogue way lactole 11 was used as starting material in a scale of 42.5 µmol. Natural product 1 (6.00 mg, 23.0 µmol, 55%) was isolated as colourless oil. TLC: R f = 0.76 (EtOAc) [UV, CAM]. S28
29 IR (ATR): ν = 3414 (b, OH), 2960 (m), 2924 (s, C-H), 2850 (m, C-H), 1665 (s, C=O), 1605 (m), 1469 (w), 1376 (w), 1119 (m), 1045 (w), 756 (w). 1 H-NMR (360 MHz, CDCl 3 ): δ (ppm) = 1.41 (s, 3H, H-4 *), 1.64 (s, 3H, H-5 *), 1.98 (dd, 2 J = 14.8 Hz, 3 J = 7.3 Hz, 1H, H-1 β), 2.47 (dd, 2 J = 14.8 Hz, 3 J = 8.2 Hz, 1H, H-1 α), 2.69 (d, 3 J = 3.4 Hz, 1H, 4-OH), 3.39 (s, 3H, NCH 3 ), 3.92 (s, 1 H, 3-OH) (m, 2H,H-2, H-4), 6.99 (d, 3 J = 7.6 Hz, 1H, H-8), 7.19 (td, 3 J = 7.6 Hz, 4 J = 1.4 Hz, 1H, H-6), 7.34 (t, 3 J = 7.6 Hz, 1H, H-7), 7.61 (dt, 3 J = 7.6 Hz, 4 J = 1.4 Hz, 1H, H-5). 13 C-NMR (126 MHz, CDCl 3 ): δ (ppm) = 17.8 (q, C-5 ), 26.1 (q, C-4 ), 28.8 (t, C-1 ), 30.4 (q, NCH 3 ), 72.8 (d, C-4), 76.1 (s, C-3), (d, C-8), (d, C-2 ), (d, C-6), (d, C-5), (s, C-4a), (d, C-7), (s, C-3 ), (s, C-8a), (s, C-2). * commutable signals. MS (EI,70 ev): m/z (%) = 261 (4) [M + ], 226 (66) [(C 15 H 16 NO) 2+ ], 192 (20) [(M-C 5 H 9 ) + ], 176 (23), 175 (32), 174 (41) [(M-C 5 H 10 O) + ], 146 (58) [(M-C 6 H 14 O 2 ) + ], 109 (45), 85 (43), 69 (55) [(C 5 H 9 ) + ], 57 (50), 55 (37), 43 (100) [(C 3 H 6 ) + ]. HRMS (EI): C 15 H 19 NO 3 calc.: [M + ]: found: [M + ]: Chiral HPLC: t R [racemate] = 11.2 min, 15.1 min; t R [ent-1] = 11.1 min, t R [1] = 15.0 min; 99% ee (AD-H, mm, n-hexane/i-proh = 90:10, 1 ml/min, λ = 210 nm). Specific rotation: [α] 20 D = 6.34 (c = 0.16, CHCl 3 ). The analytical data are in agreement with the literature (see next page). [3] S29
30 Comparison of Analytical Data (natural product/synthetic material) chart 2: Comparison between literature data and measured data for 1 H-NMR in CDCl 3. 1 H assignment natural product [3] [ppm] synthetic material [ppm] H (d, J = 7.7 Hz) 7.61 (dt, J = 7.6, 1.4 Hz) H (t, J = 7.7 Hz) 7.34 (t, J = 7.6 Hz) H (t, J = 7.7 Hz) 7.19 (td, J = 7.6, 1.4 Hz) H (d, J = 7.7 Hz) 6.99 (d, J = 7.6 Hz) H (overlapped with H-4) (m, H-2, H-4) H (overlapped with H-2 ) (m, H-2, H-4) 3-OH 3.93 (br s) 3.92 (s) N-CH (s) 3.39 (s) 4-OH 2.70 (br s) 2.69 (d, J = 3.4 Hz) H (dd, J = 14.7, 8.1 Hz) 2.47 (dd, J = 14.8, 8.2 Hz, H-1α ) H (dd, J = 14.7, 7.3 Hz) 1.98 (dd, J = 14.8, 7.3 Hz, H-1β ) 3 -CH (s) 1.64 (s) 3 -CH (s) 1.41 (s) chart 3: Comparison between literature data and measured data for 13 C-NMR in CDCl C assignment natural product [3] [ppm] synthetic material [ppm] C (s) (s) C-8a (s) (s) C (s) (s) C (d) (d) C-4a (s) (s) C (d) (d) C (d) (d) C (d) (d) C (d) (d) C (s) 76.1 (s) C (d) 72.8 (d) S30
31 N-CH (q) 30.4 (q) C (t) 28.8 (t) 3 -CH (q) 26.1 (q, C-4 ) 3 -CH (q) 17.8 (q, C-5 ) chart 4: Comparison between literature data and synthetic data for 1 H-NMR in DMSO-d 6. 1 H assignment natural product [3] [ppm] synthetic material [ppm] H (d, J = 7.8 Hz) 7.39 (d, J = 7.7 Hz) H (t, J = 7.8 Hz) 7.29 (td, J = 7.7, 1.6 Hz) H (d, J = 7.8 Hz) 7.06 (d, J = 7.7 Hz) H (t, J = 7.8 Hz) 7.07 (t, J = 7.7 Hz) 4-OH 5.65 (d, J = 4.8 Hz) 5.68 (d, J = 4.7 Hz) 3-OH 5.15 (br s) 5.20 (s) H (br t, J = 7.7 Hz) 5.06 (t, J = 7.4 Hz) H (d, J = 4.8 Hz) 4.55 (d, J = 4.7 Hz) N-CH (s) 3.24 (s) H (dd, J = 15.0, 7.7 Hz) 2.32 (dd, J = 14.9, 7.4 Hz) H (dd, J = 15.0, 7.7 Hz) 2.16 (dd, J = 14.9, 7.4 Hz) 3 -CH (s) 1.56 (s) 3 -CH (s) 1.38 (s) S31
32 2. References for the Supporting Information 1. F. Marsais, A. Godard, G. Queguiner, Journal of Heterocyclic Chemistry 1989, 26, K. Kobayashi, M. Suzuki, H. Suginome, The Journal of Organic Chemistry 1992, 57, C. Ito, M. Itoigawa, T. Otsuka, H. Tokuda, H. Nishino, H. Furukawa, Journal of Natural Products 2000, 63, S32
33 3. NMR spectra of new compounds S33
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54 S54
55 4. HPLC traces of racemic and enantioenriched products S55
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