Supporting Information Efficient Benzimidazolidinone Synthesis via Rhodium-Catalyzed Double-Decarbonylative C C Activation/Cycloaddition between Isatins and Isocyanates Rong Zeng, Peng-hao Chen, and Guangbin Dong* Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States Email: gbdong@cm.utexas.edu Table of Contents General information Preparation of starting materials Double-decarbonylative cut and sew reactions One pot reaction of isatins with azides References X-Ray data Spectra S2 S3-S5 S6-S15 S15-S18 S18 S19-S20 S21-S47 S1
Materials: 1,4-dioxane was purchased from Fischer Scientific and distilled freshly over sodium. PhCl was purchased from Alfa Aesar and distilled freshly over P 2 O 5 and freeze-pump-thawed. Other commercially available chemicals were purchased and used without additional purification unless noted otherwise. All reactions were carried out under nitrogen with stirring bar in a rubber septum sealed flask. Reaction temperatures were reported as the temperatures of the bath surrounding the flasks or vials. Sensitive reagents and solvents were transferred under nitrogen into a nitrogen-filled glove-box with standard techniques. Analytical thin-layer chromatography (TLC) was carried out using 0.2 mm commercial silica gel plates (silica gel 60, F254, EMD chemical). Vials (15 x 45 mm 1 dram (4 ml) / 27.75 x 95 mm 10 dram (40 ml) with PTFE lined cap attached) were purchased from Qorpak and flame-dried or put in an oven overnight and cooled in a dessicator. High-resolution mass spectra (HRSM) were obtained on a Karatos MS9 and are reported as m/z (relative intensity). Accurate masses are reported for the molecular ion [M+Na] +, [M+H] +, [M-H] - or [M] +. Infrared spectra were recorded on a Nicolet 380 FTIR using neat thin film technique. Nuclear magnetic resonance spectra ( 1 H NMR and 13 C NMR) were recorded with a Varian Gemini (400 MHz, 1 H at 400 MHz, 13 C at 100 MHz). Unless otherwise noted, all spectra were acquired in CDCl 3. Chemical shifts are reported in parts per million (ppm, δ), downfield from tetramethylsilane (TMS, δ=0.00 ppm), and are referenced to residual solvent (CDCl 3, δ=7.26 ppm ( 1 H) and 77.00 ppm ( 13 C)). Coupling constants were reported in Hertz (Hz). Data for 1 H NMR spectra were reported as follows: s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, dd = doublet of doublets, td = triplet of doublets, ddd = doublet of doublet of doublets, m = multiplet, coupling constant (Hz), and integration). S2
Preparation of starting materials. All the isatin derivatives were synthesized according to known procedures. [1] Ferrocenoyl azide was prepared according to known procedures. [2] 1. Preparation of 2o-P. (zr-10-42) Typical Procedure 1: To a solution of D-α-Tocoperol Succinate (1.06 g, 2.0 mmol) and DMF (1 drop) in DCM (15 ml), oxalyl chloride (0.26 ml, d = 1.455, 3.0 mmol) was added dropwise under nitrogen atmosphere. The resulting mixture was stirred at room temperature for 2.5 h and then evaporated to afford the crude product, which was used for next step directly. To a solution of prepared acyl chloride in DCM (20 ml), NaN 3 (278.1 mg, 4.3 mmol) was added. The resulting mixture was stirred at room temperature for 14 h, then diluted with DCM (50 ml), washed with NaCl (sat. aq., 20 ml 1), dried with MgSO 4. Evaporation and flash chromatograph (eluent: hexane/ethyl acetate = 30/1) afforded compound 2o-P (580.6 mg, 52%): 1 H NMR (400 MHz, CDCl 3 ) δ 2.95 (t, J = 6.4 Hz, 2H), 2.85-2.74 (m, 2H), 2.58 (t, J = 6.8 Hz, 2H), 2.09 (s, 3H), 2.01 (s, 3H), 1.98 (s, 3H), 1.88-1.69 (m, 2 H), 1.61-0.97 (m, other protons), 0.93-0.76 (m, 12 H); 13 C NMR (100 MHz, CDCl3) δ 179.0, 170.6, 149.5, 140.4, 126.6, 124.9, 123.1, 117.4, 75.0, 39.4, 37.43, 37.41, 37.40, 37.3, 32.8, 32.7, 31.6, 28.4, 28.0, 24.8, 24.4, 22.7, 22.6, 21.0, 20.6, 19.7, 19.6, 12.9, 12.1, 11.8; IR (neat, cm -1 ) 2926, 2868, 2274, 1754, 1723, 1462, 1378, 1156; HRMS (ESI) for C 33 H 53 NO 4 Na (MW = 550, (M+Na-N 2 ) + ): 550.3867. Found: 550.3870. 2. Preparation of 2b- 13 C-P. (zr-10-86b) S3
According to Typical Procedure 1, the reaction of benzoic acid- 13 C (368.8 mg, 3 mmol), DCM (15 ml), DMF (1 drop), and oxalyl chloride (0.40 ml, d = 1.455, 4.5 mmol) afforded the crude acyl chloride, which was used for next step directly. The reaction of prepared acyl chloride and NaN 3 (0.61 g, 9.4 mmol) in DCM (20 ml) afforded compound 2b- 13 C-P (221.5 mg, 50%): 1 H NMR (400 MHz, CDCl 3 ) δ 8.08-7.97 (m, 2H), 7.66-7.56 (m, 1 H), 7.51-7.40 (m, 2H); 13 C NMR (101 MHz, CDCl 3 ) δ 172.5, 134.31 (d, J = 1.1 Hz), 130.61 (d, J = 72.1 Hz), 129.44 (d, J = 2.5 Hz), 128.64 (d, J = 4.6 Hz); IR (neat, cm -1 ) 2132, 1654, 1648, 1179; HRMS (EI) for C 13 6 CH 5 ON 3 (MW = 148, M + ): 148.0466. Found: 148.0463. 3. Preparation of 4. [1,3] To a solution of 4-A (1.04 g, 4.8 mmol) in H 2 O (35 ml) and HOAc (0.6 drop), NaOCN (0.76 g) in H 2 O (10 ml) was added dropwise in 5 mins at 35 o C. The resulting mixture was stirred at 35 o C for another 0.5 h and cooled to room temperarure. NaOH (8.07 g) was then added slowly in 10 mins. After stirring for another 10 mins, TBAB (302.2 mg, 1 mmol) and MeI (1.7 ml, 30 mmol) were added. The resulting mixture was stirred at room temperature for 19 h, extracted with DCM (40 ml 3), dried with MgSO 4. Evaporation and flash chromatograph (eluent: S4
hexane/ethyl acetate = 1/1 to 1/2) afforded compound 4-B (1.07 g, 83%): 1 H NMR (400 MHz, CDCl 3 ) δ 7.48 (dd, J 1 = 7.9 Hz, J 2 =1.1 Hz, 1H), 7.43-7.35 (m, 1H), 7.16 (dd, J 1 = 8.4 Hz, J 2 = 1.1 Hz, 1H), 3.57 (s, 3H), 3.42 (s, 3H). 13 C (400 MHz, CDCl 3 ) δ 159.8, 150.4, 142.6, 134.1, 130.1, 124.0, 113.2, 113.2, 31.45 (q, J = 2.0 Hz), 28.73 (q, J = 2.0 Hz). IR (neat, cm -1 ) 1791, 1659, 1599, 1573, 1478, 1299; HRMS (ESI) for C 10 H 79 9 BrN 2 O 2 Na (MW = 291, (M+Na) + ): 290.9740. Found: 290.9740. To a dried flask were added 4-B (267.1 mg, 1.0 mmol), bis(pinacolato)diboron (288.8 mg, 1.1 mmol), Pd(dppf)Cl 2 CH 2 Cl 2 (82.2 mg, 0.1 mmol, 10 mol%), KOAc (296.6 mg, 3 mmol), and 1,4-dioxane (15 ml) under a nitrogen atmosphere. The resulting mixture was stirred at 100 o C for 17 h, then filtered through celite, washed with ethyl acetate, and evaporated to afford the crude product. Flash chromatograph (eluent: hexane/ethyl acetate = 5/1 to 2/1) afforded compound 4-C, which was used for next step directly. To a dried flask were added compound 4-C, 2-bromo-3-methylpyridine (0.25 ml, d = 1.544, 2.2 mmol), Cs 2 CO 3 (978.8mg, 3 mmol), and Pd(dppf)Cl 2 CH 2 Cl 2 (80.6 mg, 0.1 mmol, 10 mol%) in 1,4-dioxane (15 ml) under a nitrogen atmosphere. The resulting mixture was stirred at 100 o C for36 h, then filtered through celite, washed with ethyl acetate, and evaporated to afford the crude product. Flash chromatograph (eluent: ethyl acetate) afforded compound 4 (154.2mg, 55% for 2 steps): 1 H NMR (400 MHz, CDCl 3 ) δ 8.47-8.39 (m, 1H), 7.69 (dd, J 1 = 8.5, J 2 = 7.5 Hz, 1H), 7.58-7.50 (m, 1H), 7.28 (dd, J 1 = 8.5 Hz, J 2 = 1.0 Hz, 1H), 7.20 (dd, J 1 = 7.7 Hz, J 1 = 4.9 Hz, 1H), 7.04 (dd, J 1 = 7.5 Hz, J 1 = 1.0 Hz, 1H), 3.63 (s, 3H), 3.30 (s, 3 H), 2.02 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 160.8, 159.3, 150.9, 145.9, 143.1, 141.1, 136.8, 134.2, 130.6, 124.6, 122.2, 113.6, 113.1, 31.2, 28.3, 19.0; IR (neat, cm -1 ) 2925, 1706, 1659, 1593, 1501, 1431, 1376, 1311; HRMS (ESI) for C 16 H 15 N 3 O 2 Na (MW = 304, (M+Na) + ): 304.1056. Found: 304.1058. S5
The double decarbonylative cut and sew reactions of isatins 1 with isocyanates 2. Synthesis of 3aa: (zr-9-131, 137) Typical Procedure 2: To a 40 ml vial were added 1a (40.4 mg, 0.16 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (9.9 mg, 0.032 mmol). Then the vial was transferred into nitrogenfilled glovebox via standard glovebox technique. After adding isocyanate 2a (55 μl, d = 1.206, 0.48 mmol) and 1,4-dioxane (4 ml), the vial was sealed and stirred at a pre-heated pie-block at 160 o C for 48 h. Upon reaction completion, the reaction mixture was concentrated under vacuum and directly purified via flash chromatography to give the desired product 3aa (49.5 mg, 93%) (eluent: hexane/ethyl acetate = 1/3 to ethyl acetate): solid; mp: 192-194 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.27-8.18 (m, 1H), 7.24 (t, J = 7.8 Hz, 1H), 7.16-7.08 (m, 2H), 7.07-6.82 (m, 4H), 6.79-6.57 (m, 2H), 3.52 (s, 3H), 1.92 (s, 3H); 19 F NMR (376 MHz, CDCl 3 ) δ -114.30 ~ -114.43 (m); 13 C NMR (101 MHz, CDCl 3 ) δ 161.1 (d, J = 247.1 Hz), 155.0, 154.1, 146.4, 136.9, 131.8, 130.7, 130.4 (d, J = 3.1 Hz), 128.6 (brs), 126.3, 123.20, 123.15, 122.2 (d, J = 44.0 Hz), 114.7(d, J = 22.9 Hz), 107.4, 27.4, 19.1;IR (neat, cm -1 ) 3063, 1712, 1608, 1512, 1469, 1431, 1397, 1300, 1223, 1083; HRMS (ESI) for C 20 H 16 FN 3 ONa (MW = 356, (M+Na) + ): 356.1170. Found: 356.1174. The following compounds were prepared according to Typical Procedure 2. DG N O N Me DG = 3-methyl-2-pyridinyl 3ab (zr-10-20) S6
According to Typical Procedure 2, the reaction of 1a (40.0 mg, 0.16 mmol), 2b (52.5 μl, d = 1.09, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (9.9 mg, 0.032 mmol) in 1,4- dioxane (4 ml) at 160 o C for 48 h afforded 3ab (47.9 mg, 93%) (eluent: hexane/ethyl acetate = 1/2 to 1/4): Solid; 181-183 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.22-8.14 (m, 1H), 7.22 (t, J = 7.8 Hz, 1H), 7.17-6.61 (m, 9H), 3.51 (s, 3H), 1.89 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.1, 154.1, 146.2, 136.7, 134.3, 131.7, 130.7, 127.8, 126.8, 126.3, 123.3, 123.2, 122.1, 121.6, 107.2, 27.3, 19.0; IR (neat, cm -1 ) 3064, 1711, 1596, 1501, 1468, 1393, 1220, 1191, 1082; HRMS (ESI) for C 20 H 17 N 3 ONa (MW = 338, (M+Na) + ): 338.1264. Found: 338.1267. (zr-10-7) According to Typical Procedure 2, the reaction of 1a (19.9 mg, 0.08 mmol), 2c (32.3 mg, 0.24 mmol), [Rh(cod)Cl] 2 (2.1 mg, 0.004 mmol), and AsPh 3 (5.1 mg, 0.032 mmol) in PhCl (2 ml) at 160 o C for 46 h afforded 3ac (14.5 mg, 47%) (eluent: hexane/ethyl acetate = 1/1 to 1/2): Solid; 214-216 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.30-8.21 (m, 1H), 7.29 (td, J 1 = 3.9 Hz, J 2 =0.8 Hz, 1 H), 7.23-7.04 (m, 5H), 7.00 (dd, J 1 =7.7 Hz, J 2 =4.7 Hz, 1H), 6.89 (brs, 2H), 3.55 (s, 3H), 1.95 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.0, 153.8, 146.5, 137.0, 133.6, 131.8, 131.0, 130.8, 128.4, 126.2, 123.3,123.2, 122.2, 122.0, 120.6, 107.5, 27.4, 19.1; IR (neat, cm -1 ) 2926, 1712, 1618, 1491, 1467, 1393, 1296, 1221, 1081; HRMS (ESI) for C 20 H 79 17 BrN 3 O (MW = 394, (M+H) + ): 394.0550. Found: 394.0558. (zr-10-10) According to Typical Procedure 2, the reaction of 1a (40.1 mg, 0.16 mmol), 2d (93.0 mg, 0.48 S7
mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (9.9 mg, 0.032 mmol) in 1,4-dioxane (4mL) at 160 o C for 48 h afforded 3ad (60.4 mg, 98%) (eluent: hexane/ethyl acetate = 1/1.5 to 1/3): Solid; 170-173 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.21-8.14 (m, 1H), 7.67 (d, J = 8.2 Hz, 2H), 7.30-7.20 (m, 1H), 7.15-6.95 (m, 5H), 6.85 (dd, J 1 = 7.7 Hz, J 2 = 4.8 Hz, 1H), 4.32 (q, J = 7.1 Hz, 2H), 3.51 (s, 3H), 1.92 (s, 3H), 1.36 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 165.7, 154.9, 153.7, 146.5, 138.6, 137.0, 131.7, 130.9, 129.0, 128.4, 126.3, 125.9, 123.4, 123.4, 122.3, 122.1, 107.4, 60.9, 27.4, 18.9, 14.2; IR (neat, cm -1 ) 2981, 1716, 1603, 1514, 1468, 1393, 1275, 1172, 1101; HRMS (ESI) for C 23 H 21 N 3 O 3 Na (MW = 410, (M+Na) + ): 410.1475. Found: 410.1477. (zr-10-8) According to Typical Procedure 2, the reaction of 1a (40.1 mg, 0.16 mmol), 2e (79.7 mg, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (9.9 mg, 0.032 mmol) in 1,4-dioxane (4 ml) at 160 o C for 46 h afforded 3ae (57.4 mg, quant.) (eluent: hexane/ethyl acetate = 1/2 to 1/3): Solid; 188-191 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.22-8.13 (m, 1H), 7.86 (d, J = 9.0 Hz,, 2 H), 7.29 (t, J = 7.8 Hz, 1H), 7.24-6.99 (m, 5H), 6.91 (dd, J 1 = 7.7 Hz, J 2 =4.8 Hz, 1H), 3.52 (s, 3H), 1.97 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 154.8, 153.3, 146.7, 145.4, 140.5, 137.3, 131.8, 131.0, 126.8, 125.5, 123.7, 123.3, 123.0, 122.7, 122.5, 107.8, 27.5, 18.9; IR (neat, cm -1 ) 2928, 1725, 1593, 1501, 1500, 1468, 1392, 1347, 1219, 1082; HRMS (ESI) for C 20 H 17 N 4 O 3 (MW = 361, (M+H) + ): 361.1295. Found: 361.1302. (zr-10-39) S8
According to Typical Procedure 2, the reaction of 1a (40.2 mg, 0.16 mmol), 2f (83 μl, d = 1.476, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (10.5 mg, 0.032 mmol) in 1,4- dioxane (4 ml) at 160 o C for 48 h afforded 3af (69.2 mg, 96%) (eluent: hexane/ethyl acetate = 2/1 to 1/1): oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (dd, J 1 = 4.9 Hz, J 2 =1.6 Hz, 1H), 7.62-7.30 (m, 3H), 7.27-7.14 (m, 2H), 7.09 (dd, J 1 =7.9 Hz, J 2 =1.1 Hz, 1H), 7.03 (dd, J 1 =7.8 Hz,J 1 = 1.1 Hz, 1H), 6.82 (dd, J 1 =7.8 Hz, J 1 =4.8 Hz, 1H), 3.48 (s, 3H), 2.05 (s, 3H); 19 F NMR (376 MHz, CDCl 3 ) δ -62.85. 13 C NMR (100 MHz, CDCl 3 ) δ 154.1, 153.6, 146.7, 137.8, 136.5, 131.6 (q, J = 33.0 Hz), 131.5, 131.1, 127.2 (brs), 126.6, 123.6, 123.0, 122.55 (q, J = 271.0 Hz), 122.48, 122.4, 120.8 (m), 107.8, 27.5, 18.9; IR (neat, cm -1 ) 3056, 1719, 1606, 1478, 1465, 1400, 1279, 1179, 1133; HRMS (ESI) for C 22 H 15 F 6 N 3 ONa (MW = 474, (M+Na) + ): 474.1012. Found: 474.1019. (zr-10-1) According to Typical Procedure 2, the reaction of 1a (40.1 mg, 0.16 mmol), 2g (86.8 mg, 0.48 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (10.5 mg, 0.032 mmol) in 1,4-dioxane (4 ml) at 160 o C for 44 h afforded 3ag (56.3 mg, 94%) (eluent: hexane/ethyl acetate = 1/3 to ethyl acetate): Solid; 66-68 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.11 (d, J = 4.6 Hz, 1H), 7.23-7.10 (m, 2H), 7.06 (d, J = 7.8 Hz, 1H), 6.94 (d, J = 7.7 Hz, 1H), 6.85 (dd, J 1 = 7.7 Hz, J 2 = 4.8 Hz, 1H), 6.66-6.53 (m, 2H), 6.48 (d, J = 8.9 Hz, 1H), 3.62 (s, 3H), 3.56 (s, 3H), 3.51 (s, 3H), 1.98 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 154.9, 153.9, 152.7, 149.2, 145.6, 136.4, 131.8, 130.9, 126.9, 123.5, 123.3, 122.7, 122.1, 121.2, 115.8, 114.8, 111.7, 107.1, 55.6, 55.5, 27.4, 19.0; IR (neat, cm -1 ) 2936, 1715, 1512, 1471, 1452, 1389, 1301, 1229, 1175, 1080, 1044; HRMS (ESI) for C 22 H 22 N 3 O 3 (MW = 376, (M+H) + ): 376.1656. Found: 376.1660. S9
DG N O N Me DG = 3-methyl-2-pyridinyl 3ah (zr-10-22) According to Typical Procedure 2, the reaction of 1a (40.2 mg, 0.16 mmol), 2h (82.4 mg, 0.48 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (10.2 mg, 0.032 mmol) in PhCl (4 ml) at 160 o C for 48 h afforded 3ah (46.2 mg, 79%) (eluent: hexane/ethyl acetate = 1/2 to 1/4): Solid; 234-236 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.64-7.53 (m, 1H), 7.53-6.99 (m, 9 H), 6.85 (d, J = 8.7 Hz, 1H), 6.66 (brs, 1H), 6.45 (brs, 1H), 3.52 (s, 3H), 1.59 (brs, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 154.4, 154.0, 145.3, 136.1, 133.8, 131.4, 131.0, 130.2, 128.5, 127.7, 127.3, 126.4, 125.9, 124.7, 123.7, 122.9, 121.6, 121.5, 107.3, 27.5, 19.3; IR (neat, cm -1 ) 3271, 3054, 1713, 1630, 1560, 1463, 1430, 1404, 1296, 1227, 1089; HRMS (ESI) for C 24 H 19 N 3 ONa (MW = 388, (M+Na) + ): 388.1420. Found: 388.1424. (zr-9-139) According to Typical Procedure 2, the reaction of 1a (39.8 mg, 0.16 mmol), 2i (44 μl, d = 0.94, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (9.8 mg, 0.032 mmol) in 1,4- dioxane (4 ml) at 160 o C for 48 h afforded 3ai (43.3 mg, 98%) (eluent: hexane/ethyl acetate = 1/3 to ethyl acetate): oil; 1 H NMR (400 MHz, CDCl 3 ) δ 8.55-8.46 (m, 1H), 7.58 (ddd, J 1 = 7.7 Hz, J 2 =1.7 Hz, J 3 = 0.8 Hz, 1H), 7.27-7.20 (m, 1H), 7.13 (t, J = 7.8 Hz, 1H), 7.01 (dd, J 1 = 7.9 Hz, J 2 = 1.2 Hz, 1H), 6.90 (dd, J 1 = 7.7 Hz, J 2 = 1.2 Hz, 1H), 5.33 (ddt, J 1 = 17.2 Hz, J 2 = 10.3 Hz, J 3 = 5.1 Hz, 1H), 4.77 (dq, J 1 = 10.4 Hz, J 2 = 1.6 Hz, 1H), 4.52-4.38 (m, 1H), 4.23 (brs, 1H), 3.98 (brs, 1H), 3.46 (s, 3H), 2.13 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 156.2, 154.6, 146.1, 138.0, 133.0, 132.4, 131.0, 126.1, 123.0, 122.9, 122.8, 120.8, 115.7, 107.0, 44.2, 27.3, 19.6; IR (neat, cm -1 ) 3062, 2928, 1707, 1618, 1471, 1443, 1398, 1169, 1090; HRMS (ESI) for C 17 H 17 N 3 ONa (MW = 302, (M+Na) + ): 302.1264. Found: 302.1269. S10
(zr-10-65) According to Typical Procedure 2, the reaction of 1a (40.2 mg, 0.16 mmol), 2j (40μL, d = 0.89, 0.50 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (10.2mg, 0.032 mmol) in 1,4- dioxane (4 ml) at 160 o C for 48 h afforded 3aj (38.6 mg, 90%) (eluent: hexane/ethyl acetate = 1/3 to ethyl acetate): solid;v106-108 o C; 1 H NMR (400 MHz, CDCl 3 ) δ8.53-8.46 (m, 1H), 7.60 (d, J = 7.3 Hz, 1H), 7.24 (dd, J = 7.5, 4.6 Hz, 1H), 7.11 (t, J = 7.8 Hz, 1H), 6.98 (dd, J = 7.8, 0.9 Hz, 1H), 6.89 (dd, J 1 = 7.7 Hz, J 2 =0.8 Hz, 1H), 3.58-3.39 (m, 4H), 3.30 (brs, 1H), 2.14 (s, 3H), 0.76 (t, J = 7.1 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 156.3, 154.5, 146.4, 137.7, 132.5, 130.8, 125.9, 123.0, 122.7, 122.5, 120.7, 107.0, 37.0, 27.1, 19.2, 13.8; IR (neat, cm -1 ) 2975, 1707, 1473, 1449, 1400, 1383, 1082; HRMS (ESI) for C 16 H 17 N 3 ONa (MW = 290, (M+Na) + ): 290.1264. Found: 290.1267. DG N O N Me DG = 3-methyl-2-pyridinyl 3ak (zr-10-41) According to Typical Procedure 2, the reaction of 1a (39.3 mg, 0.16 mmol), 2k (59μL, d = 1.078, 0.48 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (9.9mg, 0.032 mmol) in 1,4-dioxane (4 ml) at 160 o C for 48 h afforded 3ak (48.2 mg, 94%) (eluent: hexane/ethyl acetate = 1/2 to 1/4): solid; 153-155 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (ddt, J 1 = 4.7 Hz, J 2 =1.6 Hz, J 3 = 0.7 Hz, 1H), 7.27 (ddt, J 1 = 7.8 Hz, J 1 = 1.5 Hz, J 1 = 0.8 Hz, 1H), 7.16 (dd, J = 7.7 Hz, J 1 = 4.8 Hz, 1H), 7.11 (td, J 1 = 7.8 Hz, J 2 = 0.5 Hz, 1H), 7.08-6.93 (m, 4H), 6.79 (dd, J 1 = 7.7 Hz, J 2 = 1.0 Hz, 1H), 6.46 (d, J = 7.4 Hz, 2 H), 5.21 (d, J = 16.3 Hz, 1H), 4.46 (d, J = 16.3 Hz, 1H), 3.54 (s, 3H), 1.58 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.9, 155.1, 145.6, 137.9, 136.9, 133.4, 131.2, 127.9, 126.8, 125.9, 125.6, 123.2, 123.1, 122.7, 120.8, 107.0, 45.4, 27.4, 18.9; IR (neat, cm -1 ) 3032, 1707, 1618, 1496, 1471, 1444, 1399, 1360, 1167, 1094; HRMS (ESI) for C 21 H 19 N 3 ONa S11
(MW = 352, (M+Na) + ): 352.1420. Found: 352.1425. (zr-10-17) According to Typical Procedure 2, the reaction of 1a (40.6 mg, 0.16 mmol), 2l (38μL, d = 0.898, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (10.6 mg, 0.032 mmol) in 1,4- dioxane (4 ml) at 160 o C for 44 h afforded 3al (38.7 mg, 74%) (eluent: hexane/ethyl acetate = 1/2 to 1/3): solid; 156-158 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.49 (dd, J 1 = 4.8 Hz, J 2 = 1.1 Hz, 1H), 7.56 (ddd, J 1 = 7.7 Hz, J 2 = 1.6 Hz, J 3 = 0.7 Hz, 1H), 7.23 (dd, J 1 = 7.7 Hz, J 2 = 4.8 Hz, 1H), 7.13 (t, J = 7.8 Hz, 1H), 7.01 (dd, J 1 = 7.9 Hz, J 2 = 1.1 Hz, 1H), 6.89 (dd, J 1 = 7.7 Hz, J 2 = 1.1 Hz, 1H), 4.32 (brs, 2H), 3.81 (q, J = 6.8 Hz, 2H), 3.45 (s, 3H), 2.13 (s, 3H), 1.05 (t, J = 7.1 Hz, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 167.8, 155.5, 154.5, 146.2, 138.0, 133.4, 131.0, 122.9, 122.6, 121.0, 107.3, 60.9, 43.5, 27.3, 19.5, 13.9; IR (neat, cm -1 ) 2983, 1749, 1712, 1619, 1497, 1473, 1440, 1400, 1208, 1170, 1023; HRMS (ESI) for C 18 H 19 N 3 O 3 Na (MW = 348, (M+Na) + ): 348.1319. Found: 348.1323. (zr-10-56) According to Typical Procedure 2, the reaction of 1b (37.2 mg, 0.16 mmol), 2k (60μL, d = 1.078, 0.48 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (10.5 mg, 0.032 mmol) in PhCl (4 ml) at 160 o C for 48 h afforded 3bk (35.9 mg, 73%, 94% of purity) (eluent: hexane/ethyl acetate = 1/2 to 1/3): 1 H NMR (400 MHz, CDCl 3 ) δ 8.63 (d, J = 4.8 Hz, 1H), 7.54-7.41 (m, 1H), 7.25-7.18 (m, 1H), 7.13 (t, J = 7.8 Hz, 1H), 7.08-6.84 (m, 6 H), 6.45 (d, J = 7.3 Hz, 2 H), 5.11 (s, 2 H), 3.53 (s, 3 H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.3, 155.2, 148.1, 136.7, 136.1, 131.1, 127.9, 126.6, 125.9, 125.8, 124.6, 124.6, 124.0, 122.1, 120.9, 107.4, 45.8, 27.5; IR (neat, cm -1 ) 3061, 1707, 1618, 1585, 1496, 1462, 1442, 1398, 1164, 1104; HRMS (ESI) for C 20 H 17 N 3 ONa (MW = S12
338, (M+Na) + ): 338.1264. Found: 338.1266. (zr-10-72) According to Typical Procedure 2, the reaction of 1c (37.2 mg, 0.1 mmol), 2k (37μL, d = 1.078, 0.3 mmol), [Rh(cod)Cl] 2 (2.5 mg, 0.005 mmol), and AsPh 3 (6.2mg, 0.02 mmol) in PhCl (3 ml) at 160 o C for 46 h afforded 3ck (13.9 mg, 41%) (eluent: hexane/ethyl acetate = 1.8/1): 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (d, J = 1.0 Hz, 1H), 7.76-7.67 (m, 1 H), 7.21-7.07 (m, 4H), 6.97 (dd, J 1 = 7.8 Hz, J 2 = 1.4 Hz, 1H), 6.88-6.66 (m, 4H), 6.36 (d, J = 7.2 Hz, 2H), 4.88 (s, 2H), 3.56 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 154.9, 141.5, 136.0, 135.0, 132.4, 128.6, 127.7, 127.4, 127.0, 126.7, 125.5, 125.1, 124.1, 122.2, 121.3, 121.3, 120.6, 109.9, 107.8, 45.5, 27.7; IR (neat, cm -1 ) 2926, 1712, 1618, 1483, 1416, 1400, 1379, 1166; HRMS (ESI) for C 22 H 19 N 4 O (MW = 355, (M+H) + ): 355.1553. Found: 355.1549. (zr-10-56) According to Typical Procedure 2, the reaction of 1d (24.6 mg, 0.16 mmol), 2k (37μL, d = 1.078, 0.3 mmol), [Rh(cod)Cl] 2 (2.6 mg, 0.005 mmol), and AsPh 3 (6.3 mg, 0.02 mmol) in PhCl (3 ml) at 160 o C for 48 h afforded 3dk (27.1 mg, 84%) (eluent: hexane/ethyl acetate = 1/1 to 1/3): 1 H NMR (400 MHz, CDCl 3 ) δ 8.58 (ddd, J 1 = 4.9 Hz, J 2 = 1.8 Hz, J 3 = 0.9 Hz, 1H), 7.32 (td, J 1 = 7.7 Hz, J 2 = 1.8 Hz, 1H), 7.17 (ddd, J 1 = 7.6 Hz, J 2 = 4.9 Hz, J 3 = 1.2 Hz, 1H), 7.11-7.02 (m, 3H), 6.99 (q, J = 8.0 Hz, 2H), 6.76 (dt, J 1 = 7.7 Hz, J 2 = 1.1 Hz, 1H), 6.59-6.47 (m, 2H), 5.02 (d, J = 16.8 Hz, 1H), 4.35 (d, J = 16.6 Hz, 1H), 3.50 (s, 3H), 1.96 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.7, 155.2, 148.8, 136.9, 135.4, 129.8, 128.9, 127.9, 126.59, 126.57, 126.1, 125.3, 123.6, 122.7, 122.2, 107.1, 45.3, 27.4, 19.8; IR (neat, cm -1 ) 2925, 1707, 1616, 1585, 1473, 1440, 1400, 1170, 1069; HRMS (ESI) for C 21 H 19 N 3 ONa (MW = 352, (M+Na) + ): 352.1420. Found: 352.1424. S13
(zr-10-56) According to Typical Procedure 2,the reaction of 1e (51.1 mg, 0.16 mmol), 2k (60μL, d = 1.078, 0.49 mmol), [Rh(cod)Cl] 2 (3.9 mg, 0.008 mmol), and AsPh 3 (9.9mg, 0.032 mmol) in PhCl (4 ml) at 160 o C for 46 h afforded 3ek (56.7 mg, 90%) (eluent: hexane/ethyl acetate = 2/1 to 1/1): solid; 163-165 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.53-8.47 (m, 1H), 7.43-7.26 (m, 6H), 7.18 (dd, J 1 = 7.7 Hz, J 2 = 4.8 Hz, 1H), 7.12-6.97 (m, 4H), 6.93 (dd, J 1 = 7.9 Hz, J 2 = 1.3 Hz, 1H), 6.76 (dd, J 1 = 7.7 Hz, J 2 = 1.3 Hz, 1H), 6.47 (dt, J 1 = 8.6 Hz, J 2 = 1.8 Hz, 2H), 5.31 (d, J = 20.0 Hz, 2H), 5.13 (d, J = 15.7 Hz, 1H), 4.49 (d, J = 16.2 Hz, 1H), 1.58 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.9, 155.2, 145.6, 138.0, 136.9, 136.2, 133.5, 130.4, 128.7, 128.0, 127.7, 127.4, 126.9, 126.0, 125.5, 123.4, 123.2, 122.7, 120.9, 107.9, 45.6, 45.1, 19.0; IR (neat, cm -1 ) 3032, 2927, 1705, 1604, 1465, 1442, 1405, 1358, 1176, 1028; HRMS (ESI) for C 27 H 23 N 3 ONa (MW = 428, (M+Na) + ): 428.1733. Found: 428.1738. (zr-10-71) According to Typical Procedure 2, the reaction of 1f (24.6 mg, 0.1 mmol), 2k (37μL, d = 1.078, 0.3 mmol), [Rh(cod)Cl] 2 (2.5 mg, 0.008 mmol), and AsPh 3 (6.8mg, 0.02 mmol) in PhCl (3 ml) at 160 o C for 46 h afforded 3fk (17.6 mg, 55%) (eluent: hexane/ethyl acetate = 1/2 to 1/4 to ethyl acetate): 1 H NMR (400 MHz, CDCl 3 ) δ 8.50 (d, J = 4.5 Hz, 1H), 8.05 (d, J = 5.3 Hz, 1H), 7.32 (d, J = 7.7 Hz, 1H), 7.22 (dd, J 1 = 7.7 Hz, J 2 = 4.7 Hz, 1H), 7.07 (dd, J 1 = 8.3 Hz, J 2 = 6.3 Hz, 1H), 7.00 (t, J = 7.4 Hz, 2H), 6.73 (d, J = 5.3 Hz, 1H), 6.44 (d, J = 7.3 Hz, 2H), 5.18 (brs, 1H), 4.55 (brs, 1H), 3.62 (s, 3H), 1.62 (s, 3H).; 13 C NMR (100 MHz, CDCl 3 ) δ 154.6, 153.7, 146.0, 145.0, 140.0, 138.21, 136.34, 133.1, 128.8, 128.0, 127.1, 125.6, 123.4, 120.5, 118.3, 45.2, 26.4, 18.7; IR (neat, cm -1 ) 2929, 1718, 1624, 1486, 1439, 1398, 1169; HRMS (ESI) for S14
C 20 H 18 N 4 ONa (MW = 353, (M+Na) + ): 353.1373. Found: 353.1376. One-pot reaction of isatins with organic azides. Synthesis of 3aa from 4-fluorobenzoyl azide. Typical Procedure 3: To a dried 40 ml vial were added 4-fluorobenzoyl azide (39.9 mg, 0.24 mmol) and PhCl (0.5 ml) under nitrogen atmosphere. Then the vial was sealed and heated at 110 o C. After 3 h, the resulting crude product was mixed with 1a (20.0 mg, 0.08 mmol), [Rh(cod)Cl] 2 (2.0 mg, 0.004 mmol), AsPh 3 (5.1 mg, 0.016 mmol), and 1,4-dioxane (2 ml) in glove box. The vial was sealed and stirred at a pre-heated pie-block at 160 o C for 37 h. Upon reaction completion, the reaction mixture was concentrated under vacuum and directly purified via flash chromatography to give the desired product 3aa (18.3 mg, 69%) (eluent: hexane/ethyl acetate = 1/2 to 1/3): 1 H NMR (400 MHz, CDCl 3 ) δ 8.27-8.18 (m, 1H), 7.24 (t, J = 7.8 Hz, 1H), 7.17-7.07 (m, 2H), 7.07-6.80 (m, 4H), 6.70 (brs, 2H), 3.52 (s, 3H), 1.91 (s, 3H); 19 F NMR (376 MHz, CDCl 3 ) δ -114.28 ~ -114.42 (m). The following compounds were prepared according to Typical Procedure 3. (zr-10-16) According to Typical Procedure 3, the reaction of ferrocenoyl azide (164.2 mg, 0.64 mmol) in S15
toluene (1 ml) afforded a mixture, which directly reacted with 1a (40.2 mg, 0.16 mmol), [Rh(cod)Cl] 2 (4.0 mg, 0.008 mmol), and AsPh 3 (10.2mg, 0.032 mmol) in 1,4-dioxane (4 ml) at 160 o C for 43 h afforded 3am (28.9 mg, 43%) (eluent: hexane/ethyl acetate = 2/1 to 1/1): 1 H NMR (400 MHz, CDCl 3 ) δ 8.56-8.50 (m, 1 H), 7.61 (dd, J 1 =7.7 Hz, J 2 =0.9 Hz, 1 H), 7.48 (t, J = 7.8 Hz, 1H), 7.31 (dd, J 1 = 7.7 Hz, J 2 =4.8 Hz, 1H), 6.98 (dd, J 1 =7.8 Hz, J 2 =0.9 Hz, 1H), 6.82 (dd, J 1 =7.9 Hz, J 2 =0.9 Hz, 1H), 4.92-4.84 (m, 1H), 4.63-4.56 (m, 1H), 4.43-4.39 (m, 2H), 4.25-4.23 (m, 1 H), 3.94 (s, 4H), 3.26 (s, 3H), 2.17 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.8, 157.7, 146.9, 146.3, 144.0, 136.4, 136.3, 132.8, 131.0, 124.0, 122.3, 120.2, 108.0, 98.0, 72.7, 70.3, 70.2, 69.8, 69.5, 69.3, 66.0, 25.9, 19.0; IR (neat, cm -1 ) 2925, 1707, 1603, 1582, 1459, 1363, 1301, 1087; HRMS (ESI) for C 24 H 21 N 3 OFeNa (MW = 446, (M+Na) + ): 446.0927. Found: 446.0924. (zr-12-35) According to Typical Procedure 3, the reaction of 4-acetylbenzoyl azide (57.4 mg, 0.3 mmol) in PhCl (1 ml) afforded a mixture, which directly reacted with 1a (24.4 mg, 0.1 mmol), [Rh(cod)Cl] 2 (2.6 mg, 0.005 mmol), and AsPh 3 (6.6 mg, 0.02 mmol) in 1,4-dioxane (3 ml) at 160 o C for 48 h afforded 3an (23.4 mg, 68%) (eluent: hexane/ethyl acetate = 2/1 to 1/1 to ethyl acetate): 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (d, J = 4.7 Hz, 1H), 7.60 (d, J = 8.2 Hz, 2H), 7.32 7.25 (m, 1H), 7.15 7.05 (m, 5H), 6.87 (dd, J = 7.7, 4.8 Hz, 1H), 3.54 (s, 3H), 2.51 (s, 3H), 1.95 (s, 3H).; 13 C NMR (100 MHz, CDCl 3 ) δ 197.18, 155.15, 153.86, 146.65, 138.97, 137.25, 135.08, 131.95, 131.11, 128.05, 126.66, 126.05, 123.69, 123.53, 122.42, 122.41, 107.75, 27.63, 26.77, 19.16; IR (neat, cm -1 ) 2925, 1712, 1683, 1600, 1468, 1429, 1391, 1267, 1175, 1082, 914, 841, 787, 732; HRMS (ESI) for C 22 H 19 N 3 O 2 Na (MW = 380, (M+Na) + ): 380.1369. Found: 380.1372. S16
(zr-10-48) According to Typical Procedure 3, the reaction of 2o-P(166.6 mg, 0.3 mmol) in PhCl (1 ml) afforded 2o, which direcly reacted with 1a (24.8 mg, 0.1 mmol), [Rh(cod)Cl] 2 (2.6 mg, 0.005 mmol), and AsPh 3 (6.3 mg, 0.02 mmol) in 1,4-dioxane (3 ml) at 160 o C for 48 h afforded 3ao (60.8 mg, 85%) (eluent: hexane/ethyl acetate = 3/1 to 1/1): oil; 1 H NMR (400 MHz, CDCl 3 ) δ 8.52 (dd, J 1 = 4.9 Hz, J 2 = 1.6 Hz, 1H), 7.65-7.59 (m, 1H), 7.25-7.20 (m, 1H), 7.17 (d, J = 7.8 Hz, 1H), 7.04 (dd, J 1 =7.9 Hz, J 2 = 1.2 Hz, 1H), 6.95 (dd, J 1 = 7.7 Hz, J 2 = 1.2 Hz, 1H), 3.99 (brs, 2H), 3.48 (s, 3H), 2.79-2.46 (m, 4H), 2.21 (s, 3H), 2.06 (s, 3H), 1.89 (s, 3H), 1.85 (s, 3H), 1.81-1.71 (m, 2H), 1.62-0.93 (m, all other protons), 0.95-0.74 (m, 12H); 13 C NMR (100 MHz, CDCl 3 ) δ168.9, 155.9, 154.5, 149.3, 146.8, 140.1, 138.1, 132.6, 131.0, 126.4, 125.7, 124.7, 123.4, 122.93, 122.90, 122.6, 121.2, 117.3, 107.3, 75.0, 39.3, 37.9, 37.4, 37.4, 37.3, 32.8, 32.7, 32.5, 28.0, 27.3, 24.8, 24.4, 22.7, 22.6, 21.0, 20.5, 19.7, 19.6, 19.3, 13.1, 12.2, 11.8; IR (neat, cm -1 ) 2926, 1753, 1711, 1460, 1385, 1146; HRMS (ESI) for C 46 H 65 N 3 O 4 Na (MW = 746, (M+Na) + ): 746.4867. Found: 746.4859. (zr-11-16) According to Typical Procedure 3, the reaction of 2b- 13 C-P (50.0 mg, 0.34 mmol) in PhCl (0.7 ml) at 100 o C for 2 h afforded 2b- 13 C, which directly reacted with 1a (25.3 mg, 0.1 mmol), [Rh(cod)Cl] 2 (2.5 mg, 0.005 mmol), and AsPh 3 (6.8mg, 0.02 mmol) in 1,4-dioxane (3 ml) at 160 o C for 48 h afforded 3ab- 13 C (27.5 mg, 87%) (eluent: hexane/ethyl acetate = 1/2 to 1/4): solid; 180-182 o C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.20 (dd, J 1 = 4.9 Hz, J 2 = 1.6 Hz, 1H), 7.24 (t, J = 7.8 Hz, 1H), 7.18-6.89 (m, 8H), 6.86 (dd, J 1 = 7.7 Hz, J 2 =4.8 Hz, 1H), 3.53 (d, J = 3.1 Hz, 3H), S17
1.90 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 155.1, 154.1, 146.2, 136.7, 134.3 (d, J = 1.5 Hz), 131.7, 130.7 (d, J = 5.7 Hz), 127.8, 126.8, 126.4 (d, J = 6.2 Hz), 123.3 (d, J = 3.3 Hz), 123.2, 122.1, 121.7, 107.2 (d, J = 3.4 Hz), 27.3 (d, J = 1.7 Hz), 19.0; IR (neat, cm -1 ) 3063, 2926, 1671, 1619, 1596, 1501, 1468, 1386, 1296, 1220, 1191, 1082; HRMS (ESI) for C 13 19 CH 17 N 3 ONa (MW = 339, (M+Na) + ): 339.1297. Found: 339.1302. References: [1] Zeng, R.; Dong, G. J. Am. Chem. Soc. 2015, 137, 1408-1411. [2] Cormode, D. P.; Evans, A. J.; Davis, J. J.; Beer, P. D. Dalton Trans.,2010, 39, 6532-6541. [3] For synthesis of 5-bromoquinazoline-2,4(1H,3H)-dione, see: Bristol-Myers Company; Johnson, J. A.; Lloyd, J.; Finlay, H.; Jiang, J.; Neels, J.; Dhondi, N. K.; Gunaga, P.; Banerjee, A.; Adisechan, A. Patent: WO2011/28741 A1, 2011. S18
Identification code ZR-9-111-1 Empirical formula C20 H16 F N3 O Formula weight 333.36 Temperature 100(2) K Wavelength 0.71075 Å Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 13.206(5) Å = 90. b = 7.219(2) Å = 102.062(4). c = 17.366(6) Å = 90. Volume 1619.1(9) Å 3 Z 4 Density (calculated) 1.368 Mg/m 3 Absorption coefficient 0.095 mm -1 F(000) 696 Crystal size 0.700 x 0.600 x 0.470 mm 3 Theta range for data collection 2.399 to 30.947. Index ranges -14<=h<=19, -10<=k<=10, -24<=l<=24 Reflections collected 28706 Independent reflections 4765 [R(int) = 0.0454] Completeness to theta = 25.242 98.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.9344 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4765 / 0 / 228 Goodness-of-fit on F 2 1.056 Final R indices [I>2sigma(I)] R1 = 0.0472, wr2 = 0.1264 R indices (all data) R1 = 0.0481, wr2 = 0.1274 Extinction coefficient n/a Largest diff. peak and hole 0.342 and -0.279 e.å -3 S19
Identification code ZR-10-17 Empirical formula C18 H19 N3 O3 Formula weight 325.36 Temperature 100(2) K Wavelength 0.71075 Å Crystal system Monoclinic Space group P 21/n Unit cell dimensions a = 10.383(3) Å = 90. b = 10.981(3) Å = 106.941(5). c = 14.706(5) Å = 90. Volume 1604.1(9) Å 3 Z 4 Density (calculated) 1.347 Mg/m 3 Absorption coefficient 0.094 mm -1 F(000) 688 Crystal size 0.460 x 0.190 x 0.120 mm 3 Theta range for data collection 2.138 to 31.117. Index ranges -15<=h<=14, -15<=k<=15, -20<=l<=19 Reflections collected 16875 Independent reflections 4641 [R(int) = 0.0357] Completeness to theta = 25.242 99.5 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.7596 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4641 / 0 / 220 Goodness-of-fit on F 2 0.963 Final R indices [I>2sigma(I)] R1 = 0.0403, wr2 = 0.0973 R indices (all data) R1 = 0.0535, wr2 = 0.1046 Extinction coefficient n/a Largest diff. peak and hole 0.295 and -0.275 e.å -3 S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31
S32
MeO DG OMe N O N Me DG = 3-methyl-2-pyridinyl 3ag S33
S34
S35
S36
S37
S38
S39 (94% of purity)
S40
S41
S42
S43
S44
S45
S46
S47