Supplementary Figure S1 X-ray crystallographic structure of (C)-(-)-6. (a) ORTEP drawing of (C)-(-)-6 at probability ellipsoids of 50%: tope view. (b) Side view. All hydrogen atoms are omitted for clarity. S1
Supplementary Figure S2 Bowl depths of (a) (C)-(-)-6 and (b) sumanene. The bowl depths were measured between the centroid of central benzene ring and that of focused atoms. S2
Supplementary Figure S3 Optimized bowl structure of compound (C)-(-)-1 by DFT calculation (B3LYP/6-311+G (d, p). (a) Side view. (b) Top view. Cartesian coordinates are listed in Supplementary Table S3. E (RB3LYP) = -2168.356546 a.u.; Zero-point correction = 0.308476 a.u.; Sum of electronic and zero-point energy E bowl = -2168.048070 a.u. S3
Supplementary Figure S4 Optimized flat structure of compound 1 corresponding to the transitional state of the bowl inversion with one imaginary frequency by DFT calculation (B3LYP/6-311+G (d, p). (a) Side view. (b) Top view. Cartesian coordinates are listed in Supplementary Table S4. E (RB3LYP) = -2168.290412 a.u.; Zero-point correction = 0.305855 a.u.; Sum of electronic and zero-point energy E flat = -2167.984557 a.u. The calculated bowl inversion energy ΔE = E flat E bowl = -2167.984557 (-2168.048070) = 39.9 kcal/mol. S4
Supplementary Figure S5 CD and UV-Vis spectra of compound 6 in CH 2 Cl 2 (5.0 10-5 M). S5
Supplementary Figure S6 (a) 1 H and (b) 13 C NMR spectra of compound 4. S6
Supplementary Figure S7 (a) 1 H and (b) 13 C NMR spectra of compound 7. S7
Supplementary Figure S8 (a) 1 H and (b) 13 C NMR spectra of compound 8. S8
Supplementary Figure S9 (a) 1 H and (b) 13 C NMR spectra of compound 5. S9
Supplementary Figure S10 (a) 1 H and (b) 13 C NMR spectra of compound (C)-(-)-1. S10
Supplementary Figure S11 (a) 1 H and (b) 13 C NMR spectra of compound (C)-(-)-6. S11
Supplementary Tables Supplementary Table S1 Screening of oxidative aromatization from compound 5 to (C)-(-)-1 by using different oxidants. a,b Determined by 1 H NMR using of mesitylene as an internal standard; c Microwave assisted reaction; d Isolated yield by PTLC. DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone. S12
Supplementary Table S2 Screening of oxidative aromatization from compound 5 to (C)-(-)-1 by using of trityl cationic reagents. Entry a Oxidant Base Yield/% b 1 Ph 3 CPF 6-0 2 Ph 3 CB(C 6 F 5 ) 4 - < 5 3 Ph 3 COH-TFA c - 0 4 Ph 3 CBF 4-25 5 Ph 3 CBF 4 i-pr 2 EtN < 5 6 Ph 3 CBF 4 Proton sponge d < 5 7 Ph 3 CBF 4 pyridine 0 8 Ph 3 CBF 4 2,6-lutidine 40 9 e Ph 3 CBF 4 DTBMP f 77 10 g Ph 3 CBF 4 DTBMP 73 h a The reactions were carried out in anhydrous CH 2 Cl 2 at 25 C for 12 h by using of 900 mol% oxidant and 330 mol% base (if used). b NMR yield using mesitylene as an internal standard. c TFA = trifluoroacetic acid. d Proton sponge = N,N,N,N -tetramethyl-1,8- naphthalenediamine. e The reaction took 3 days for completion. f DTBMP = 2,6-di-tert- butyl-4-methylpyridine. g 600 mol% Ph 3 CBF 4 and 800 mol% DTBMP were used and the reaction was completed within 8 h. h Isolated yield. S13
Supplementary Table S3 Cartesian Coordinates of compound (C)-(-)-1 by DFT calculation (B3LYP/6-311+G (d, p)). Center Number Atom Type Coordinates (Angstroms) X Y Z 1 C -0.422637-1.34611-1.35439 2 C 0.976059-1.023027-1.387835 3 C 1.377084 0.307041-1.35439 4 C 0.397938 1.356805-1.387835 5 C -0.954447 1.039069-1.35439 6 C -1.373997-0.333778-1.387835 7 C 0.847101 2.434445-0.626411 8 N 0 3.285673-0.052911 9 C -1.332399 3.008128-0.092307 10 C -1.86479 1.82444-0.649085 11 C -2.531842-0.483612-0.626411 12 N -2.845476-1.642836-0.052911 13 C -1.938916-2.657956-0.092307 14 C -0.647616-2.527175-0.649085 15 C 1.684741-1.950833-0.626411 16 N 2.845476-1.642836-0.052911 17 C 3.271315-0.350173-0.092307 18 C 2.512406 0.702736-0.649085 19 C -3.074318 0.928345-0.294193 20 C 2.341129 2.198265-0.294193 21 C 0.733189-3.12661-0.294193 22 H -3.973843 1.169282-0.871571 23 H -3.340529 1.006625 0.762623 24 H 2.542028 2.389671 0.762623 S14
25 H 2.999549 2.856808-0.871571 26 H 0.974293-4.02609-0.871571 27 H 0.798502-3.396296 0.762623 28 S -2.445021 4.116712 0.731143 29 S -2.342667-4.175806 0.731143 30 S 4.787687 0.059094 0.731143 31 C -3.869573-3.744169 1.629193 32 H -4.161275-4.652961 2.15686 33 H -3.684154-2.941537 2.34088 34 H -4.651223-3.447525 0.933476 35 C -1.307759 5.223233 1.629193 36 H -1.948945 5.93025 2.15686 37 H -0.705369 4.661339 2.34088 38 H -0.660033 5.75184 0.933476 39 C 5.177332-1.479064 1.629193 40 H 6.11022-1.277289 2.15686 41 H 4.389522-1.719802 2.34088 42 H 5.311256-2.304314 0.933476 S15
Supplementary Table S4 Cartesian Coordinates of flat 1 by DFT calculation (B3LYP/6-311+G (d, p)). Center Number Atom Type Coordinates (Angstroms) X Y Z 1 C 1.203561 0.674949 0 2 C 0 1.367116 0 3 C -1.186303 0.70484 0 4 C -1.183957-0.683558 0 5 C -0.017258-1.379789 0 6 C 1.183957-0.683558 0 7 C -2.40665-1.264 0 8 N -2.416532-2.620201 0 9 C -1.219608-3.322612 0 10 C 0.101974-2.736464 0 11 C 2.297981-1.45222 0 12 N 3.477427-0.782678 0 13 C 3.48727 0.605094 0 14 C 2.31886 1.456545 0 15 C 0.108669 2.71622 0 16 N -1.060894 3.402879 0 17 C -2.267662 2.717517 0 18 C -2.420835 1.27992 0 19 C 1.706175-2.961189 0 20 C -3.417552 0.003003 0 21 C 1.711377 2.958185 0 22 H 2.033464-3.518311 0.880898 23 H 2.033464-3.518311-0.880898 24 H -4.063679-0.001876 0.880898 25 H -4.063679-0.001876-0.880898 S16
26 H 2.030215 3.520187 0.880898 27 H 2.030215 3.520187-0.880898 28 S -1.327854-5.094157 0 29 S 5.075596 1.397123 0 30 S -3.747742 3.697034 0 31 C -3.124385-5.395424 0 32 H -3.584362-4.970964-0.890079 33 H -3.233946-6.480544 0 34 H -3.584362-4.970964 0.890079 35 C -3.110382 5.403508 0 36 H -2.512801 5.58963-0.890079 37 H -3.995342 6.040951 0 38 H -2.512801 5.58963 0.890079 39 C 6.234766-0.008085 0 40 H 7.229289 0.439592 0 41 H 6.097162-0.618666 0.890079 42 H 6.097162-0.618666-0.890079 S17
Supplementary Methods Nomenclature of chiral buckybowls Official stereodescriptor system for the absolute configuration of chiral buckybowls has not been established yet. In this paper, we use the stereodescriptor system based on fullerene nomenclature described as C or A 23-25. Another system was proposed by L. T. Scott described as M or P 31. Bowl inversion kinetic equation where a is the initial concentration of (C)-(-)-1 assigned as 1, and x is the concentration of (A)-(+)-1 at time t. Synthesis and characterization of compound 4 to 5. (1aS,3aR,4aS,6aR,7aS,9aR)-2,5,8-tris(4-methoxybenzyl)-1a,2,3a,4,4a,5,6a,7,7a,8-decahydro -1H-2,5,8-triazatricyclopenta[def,jkl,pqr]triphenylene-3,6,9(9aH)-trione (4) S18
A mixture of 3 (1.36 g, 2.0 mmol) in AcOH (140 ml) and conc. HCl (50 ml) was heated to 60 o C for 4 h. After cooling, the mixture was evaporated to afford white solid, which was then dissolved in anhydrous DMF (100 ml). To the solution was added DIPEA (7 ml, 40.0 mmol) and the solution was cooled to 0 o C under Ar atmosphere. Then FDPP (6.9 g, 18.0 mmol) in DMF (25 ml) was added. After addition, the mixture was stirred at 0 o C, 10 o C, 20 o C and 30 o C for 1 h, respectively, and then heated to 60 o C for 2 h. Evaporation of DMF afforded a residue and 1 M NaOH solution (150 ml) was added. The mixture was extracted with CH 2 Cl 2 (3 100 ml) and the combined organic layer was washed with brine, dried over Na 2 SO 4, filtered, and evaporated. The crude product was purified by silica gel chromatography (5-10% MeOH/CH 2 Cl 2 ). The resulting tan solid was stirred with EtOAc (20 ml) for 10 min and filtered, washed with EtOAc (3 5 ml) and dried to give compound 4 as an off-white solid (0.80 g, 59%). [ ] : -36.6 (c = 1.0, CHCl 3); mp: >250 o C (decomp.); IR (KBr): 2934, 1635, 1512, 1439, 1400, 1302, 1248, 1176, 1032, 817 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ): 7.27 (d, J = 8.4 Hz, 6H), 6.87 (d, J = 8.4 Hz, 6H), 5.51 (d, J = 14.6 Hz, 3H), 5.04-4.98 (m, 3H), 4.06-3.98 (m, 3H), 3.80 (s, 9H), 3.70 (d, J = 14.6 Hz, 3H), 3.30-3.22 (m, 3H), 1.92-1.82 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ): 170.1, 159.1, 141.0, 139.4, 129.8, 128.5, 114.1, 60.4, 55.2, 46.0, 43.9, 42.8; HRMS (EI) m/z Calcd for C 42 H 39 N 3 O 6 (M + ): 681.2839; Found: 681.2822. (1aS,3aR,4aS,6aR,7aS,9aR)-2,5,8-tris(4-methoxybenzyl)-1a,2,3a,4,4a,5,6a,7,7a,8-decahydro -1H-2,5,8-triazatricyclopenta[def,jkl,pqr]triphenylene-3,6,9(9aH)-trithione (7) S19
A solution of compound 4 (0.19 g, 0.279 mmol) and Lawesson s reagent (0.564 g, 0.140 mmol) in dichloroethane (10 ml) was loaded into a microwave instrument vial (10-20 ml). The vial was evacuated and flushed with argon and sealed. The mixture was irradiated with stirring at a fixed temperature of 160 o C for 40 min on a Biotage Initiator microwave apparatus. Upon completion of the reaction time, the vial was cooled with a stream of air and opened. The mixture was purified by silica gel column chromatography (0-5% EtOAc/CH 2 Cl 2 ) to afford compound 7 (0.187 g, 92%). [ ] : -301.0 (c = 1.0, CHCl 3); mp: > 250 o C (decomp.); IR (KBr): 2937, 1612, 1510, 1412, 1251, 1175, 1035, 814 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ): 7.41 (d, J = 8.6 Hz, 6H), 6.90 (d, J = 8.6 Hz, 6H), 6.83 (d, J = 14.6 Hz, 3H), 4.95-5.05 (m, 3H), 4.38-4.48 (m, 3H), 4.10 (d, J = 14.6 Hz, 3H), 3.81 (s, 9H), 3.63-3.58 (m, 3H), 2.17-2.11 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ): 201.5, 159.8, 140.4, 138.5, 129.9, 127.1, 114.6, 62.4, 55.5, 52.5, 52.4, 47.8; HRMS (EI) m/z Calcd for C 42 H 39 N 3 O 3 S 3 (M + ): 729.2154; Found: 729.2169. (1aS,3aR,4aS,6aR,7aS,9aR)-1a,2,3a,4,4a,5,6a,7,7a,8-decahydro-1H-2,5,8-triazatricyclopent a[def,jkl,pqr]triphenylene-3,6,9(9ah)-trithione (8) A solution of compound 7 (310 g, 0.425 mmol) in TFA (10 ml) was loaded in a microwave instrument vial (10-20 ml) and sealed. The solution was irradiated with stirring at a fixed temperature of 100 o C for 2 h on a microwave apparatus. On completion of the reaction time S20
the vial was cooled with a stream of air and opened. Some white precipitation was observed. After evaporation of TFA, to the resulting solid was added CH 2 Cl 2 and the mixture was stirred for 10 min. The white solid was collected by filtration and washing with CH 2 Cl 2 (3 5 ml) to afford pure compound 8 (138 mg, 88%). [ ] : -250.2 (c = 0.2, DMSO); mp: > 260 o C (decomp.); IR (KBr): 3268, 2998, 2867, 1647, 1506, 1312, 1145, 1077, 802, 736, 707 cm -1 ; 1 H NMR (400 MHz, DMSO-d 6 ): 10.6 (br s, 3H), 5.10-5.03 (m, 3H), 427-4.23 (m, 3H), 3.26-3.18 (m, 3H), 1.74-1.65 (m, 3H); 13 C NMR (100 MHz, DMSO-d 6 ): 202.2, 140.8, 138.9, 58.7, 50.2, 45.5; HRMS (EI) m/z Calcd for C 18 H 15 N 3 S 3 (M + ): 369.0428; Found: 369.0423. (1aS,3aR,4aS,6aR,7aS,9aR)-3,6,9-tris(methylthio)-1a,3a,4,4a,6a,7,7a,9a-octahydro-1H-2,5,8 -triazatricyclopenta[def,jkl,pqr]triphenylene (5) To a suspension of compound 8 (260 mg, 0.706 mmol) and K 2 CO 3 (974 mg, 7.06 mmol) in DMF (60 ml) was added MeI (1.34 ml, 21.5 mmol). The mixture was stirred for 4 h at ambient temperature. DMF was removed by evaporation (< 45 o C) and to the residue was partitioned H 2 O (10 ml) and CH 2 Cl 2 (30 ml). The aqueous layer was extracted twice with CH 2 Cl 2 (10 ml). The combined organic layer was washed with brine (20 ml), dried over Na 2 SO 4, filtered, and evaporated. The residue was purified by PTLC (7% EtOAc/CH 2 Cl 2 ) to give compound 5 as a white solid (228 mg, 79%). [ ] : 127.5 (c = 1.0, CHCl 3); mp: > 260 o C (decomp.); IR (KBr): 2958, 2925, 2876, 1645, 1582, 1438, 1296, 1124, 1040, 1005, 938 cm -1 ; 1 H NMR (400 MHz, CDCl 3 ): 5.14 (ddd, J = 7.5, 7.5, 7.5 Hz, 3H), 3.78 (ddd, J = 8.0, 8.0, 8.0 Hz, 3H), 3.40 (ddd, J = 13.1. 8.0, 8.0 Hz, 3H), 1.55 (ddd, J = 13.1, 8.4, 8.4 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ): 167.0, 142.8, 140.2, 65.0, 44.3, 43.8, 12.4; HRMS (EI) m/z Calcd for C 21 H 21 N 3 S 3 (M + ): 411.0898; Found: 411.0885. S21