Supporting Information

Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2017 Modular Synthesis of Propargylamine Modified Cyclodextrins by a Gold(III)-catalyzed Three Component Coupling Reaction Tsz-Wai Hui a,b, Jian-Fang Cui a,b and Man Kin Wong* a,b a. The Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen, PR China. b. State Key Laboratory of Chirosciences and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, PR China. These authors contributed equally to this work E-mail: mankin.wong@polyu.edu.hk Fax: +852 2364 9932 Supporting Information S1

Literature references of modified β-cyclodextrins H.-S. Byun, N. Zhong, R. Bittman, rg. Synth. 2000, 77, 225-230. 6-Ts-β-CD C. Wang, F. Chen, X.-W. He, S.-Z. Kang, C.-C. You, Y. Liu. Analyst. 2001, 126, 1716-1720. 1a S2

General Method: Chemicals were purchased from commercial sources and were used without further purification. 1-(p-Toluenesulfonyl)imidazole and 6--p-toluenesulfonyl-β-cyclodextrin (6-Ts-β-CD) were synthesized by following the literature procedure (rg. Synth. 2000, 77, 225-230). 1 H, 13 C and 2D NMR spectra were performed at 600 MHz and 150 MHz on Bruker DPX-600 spectrometer. Chemical shifts (ppm) were referenced to residual solvent or TMS signals and coupling constants are given in Hz. Data for 1 H NMR were recorded as follows: chemical shift (δ, ppm), multiplicity (s, singlet; brs, broad singlet; d, doublet; dd, double doublet; t, triplet; td, triple doublet; tt, triple triplet; q, quartet; qd, quadruple doublet, m, multiplet), coupling constant (Hz), integration. Data for 13 C NMR are reported in terms of chemical shift (δ, ppm). Low resolution and high resolution mass spectra were measured on LCQ Advantage Mass, Waters 7890A and Waters Q-TF 2TM spectrometer. Infrared spectroscopy was conducted using Nicolet 380 FT- IR. General Procedure for Synthesis of Mono-(6-benzylamino-6-deoxy)-β-cyclodextrin 1 H H H H H Ts H 6-Ts- -CD R 1 70 o C, 16 h NH 2 R 1 NH H H H H 1a: (83%), R 1 =H 1b: (60%), R 1 =CH 3 H 1c: (50%), R 1 =CH 3 1d: (36%), R 1 =Cl H 1 Scheme S1. Synthesis of mono-(6-benzylamino-6-deoxy)-β-cyclodextrin 1 6--p-Toluenesulfonyl-β-cyclodextrin (3.0 g, 2.33 mmol) was heated in benzyl amine (20 ml) at 70 o C with stirring overnight. The resulting solution was added dropwise into excess acetone (150 ml). The resulting suspension was filtered to collect yellow solid. The yellow solid was then dissolved in water and heated up until all solid was dissolved. The solution was standed for overnight to allow precipitation of solid. The suspension was filtered to collect white solid. The S3

white solid was dried to constant weight under reduced pressure to give the corresponding mono- (6-benzylamino-6-deoxy)-β-cyclodextrins 1a-1d with moderate to good yield (36-83%). General Procedure for Synthesis of Mono-(6-(benzylpropargyl)amino-6-deoxy)-βcyclodextrin 2 Scheme S2. Synthesis of mono-(6-(benzylpropargyl)amino-6-deoxy)-β-cyclodextrin 2 Mono-(6-benzylamino-6-deoxy)-β-cyclodextrin 1 (1.0 equiv.), formaldehyde (10.0 equiv.), alkyne (10.0 equiv.) and potassium gold(iii) chloride KAuCl4 (2.5 mol%) were heated in water (10 ml) at 40 o C for 24 h. The resulting suspension was filtered to collect the solid. The solid was then dissolved in water and heated at 80 o C for 20 min. The insoluble solid was removed by filtration. The solution was allowed to stand in air and precipitate for few days. The suspension was filtered to collect the white solid. The white solid was dried to constant weight under reduced pressure to give the corresponding mono-(6-benzylpropargylamino-6-deoxy)-βcyclodextrin 2a-2h with moderate to good yield (26-67%). S4

Table S1 Attempt of gold(iii) catalyzed three component coupling reaction of primary amine modified β-cyclodextrin, phenylacetylene and various aldehydes. [a] Entry R Catalyst Solvent Yield of 2aa (%) [b] 1 H KAuCl4 H2 0 2 Ph KAuCl4 H2 0 3 4-MeC6H4 KAuCl4 H2 0 4 4-N2C6H4 KAuCl4 H2 0 5 PhCH2CH2 KAuCl4 H2 0 6 CH3 KAuCl4 H2 0 7 n-c3h7 KAuCl4 H2 0 8 n-c6h13 KAuCl4 H2 0 [a] Reaction conditions: 1aa (0.1 mmol), aldehyde (1.0 mmol), phenylacetylene (1.0 mmol), 40 o C, 24 h. [b] Detected by ESI-MS and TLC analysis. Scheme S3. Proposed reaction mechanism S5

Characterization Data of Mono-(6-benzylamino-6-deoxy)-β-cyclodextrin 1 and Mono-(6- benzylpropargylamino-6-deoxy)-β-cyclodextrin 2 White solid; 60% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.19 (d, J = 7.8 Hz, 2H, Ar-H), 7.10 (d, J = 7.9 Hz, 2H, Ar- H), 5.87 5.67 (m, 15H, -2, -3, NH), 4.83-4.83 (m, 7H, H-1), 4.63 4.46 (m, 6H, -6), 3.77 3.26 (m, 42H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1 ), 2.90 (d, J = 11.7 Hz, 1H, H-6a ), 2.72 (dd, J = 12.2, 6.8 Hz, 1H, H-6b ), 2.28 (s, 3H, CH3); 13 C NMR (150 MHz, d 6 -DMS): δ 138.4, 135.8, 129.1, 128.2, 102.8, 102.4, 102.3, 102.2, 84.2, 82.00, 81.96, 81.93, 81.8, 73.5 72.5, 71.0, 60.3 60.2, 53.3, 49.5, 21.2; IR (cm -1, KBr): 3414, 2927, 1653, 1636, 1560, 1541, 1502, 1458, 1419, 1374, 1157, 1079, 1031, 948, 756, 706, 582; MS (ESI): m/z 1238.5 ([M+H] + ); HRMS (ESI): Calcd. For C50H80N35 + 1238.4483, found 1238.4552. White solid; 50% yield; S6

1 H NMR (600 MHz, d 6 -DMS): δ 7.22 (d, J = 8.1 Hz, 2H, Ar-H), 6.86 (d, J = 8.2 Hz, 2H, Ar- H), 5.84-5.71 (m, 15H, -2, -3, NH), 4.84 (s, 7H, H-1), 4.54 (m, 6H, -6), 3.73 (s, 3H, Me), 3.72 3.26 (m, 42H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1 ), 2.90 (d, J = 11.4 Hz, 1H, H- 6a ), 2.72 (s, 1H, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 158.4, 133.4, 129.4, 113.9, 102.8, 102.4, 102.34, 102.29, 84.2, 82.0, 81.9, 81.83, 81.82, 73.5 72.5, 71.0, 60.4 60.2, 55.5, 52.9, 49.3; IR (cm -1, KBr): 3366, 2929, 1637, 1514, 1420, 1368, 1302, 1247, 1156, 1079, 1031, 947, 757, 707, 582; MS (ESI): m/z 1254.4 ([M+H] + ); HRMS (ESI): Calcd. For C50H80N35 + 1254.4433, found 1254.4523. White solid; 36% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.35 (s, 4H, Ar-H), (5.85 (d, J = 6.5 Hz, 1H), 5.81 5.68 (m, 13H), -2, -3), 4.92 4.74 (m, 7H, H-1), 4.62 4.39 (m, 6H, -6), 3.83 3.20 (m, 42H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1 ), 2.90 (d, J = 11.4 Hz, 1H, H-6a ), 2.73 (dd, J = 11.8, 6.7 Hz, 1H, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 140.6, 131.4, 130.0, 128.4, 102.8, 102.43, 102.40, 102.38, 102.3, 84.2, 82.02, 81.97, 81.93, 81.85, 73.5 72.5, 71.0, 60.4 60.2, 52.6, 49.3; IR (cm -1, KBr): 3373, 2928, 1637, 1492, 1410, 1368, 1300, 1244, 1205, 1156, 1079, 1031, 947, 858, 757, 706, 581, 531; MS (ESI): m/z 1258.4 ([M+H] + ); HRMS (ESI): Calcd. For C49H77ClN34 + 1258.3937, found 1258.4048. S7

White solid; 50% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.47 (dd, J = 6.5, 2.8 Hz, 2H, Ar-H), 7.43 7.38 (m, 3H, Ar- H), 7.34 (dt, J = 15.1, 7.4 Hz, 4H, Ar-H), 7.24 (t, J = 7.0 Hz, 1H, Ar-H), 5.98 (d, J = 6.4 Hz, 1H, -2 or -3), 5.83-5.72 (m, 13H, -2, -3), 4.96 (d, J = 3.1 Hz, 1H, H-1), 4.86 4.84 (m, 6H, H-1), 4.53 4.48 (m, 6H, -6), 3.93 3.24 (m, 44H, H-2, H-3, H-4, H-5, H-6a, H-6b, H- 1, H-2 ), 3.04 2.85 (m, 2H, H-6a, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 139.5, 131.9, 129.1, 128.73, 128.70, 127.4, 123.2, 102.8, 102.6, 102.5, 102.4, 102.1, 86.1, 85.4, 84.2, 82.1, 81.94, 81.88, 81.8, 81.6, 73.7 72.5, 60.4 60.2, 58.6, 54.3, 43.5; IR (cm -1, KBr): 3384, 2927, 1637, 1491, 1419, 1369, 1156, 1079, 1029, 947, 862, 757, 701, 581, 528; MS (ESI): m/z 1338.5 ([M+H] + ); HRMS (ESI): Calcd. For C58H84N34 + 1338.4796, found 1338.4874. White solid; 51% yield; S8

1 H NMR (600 MHz, d 6 -DMS): δ 7.49-7.46 (m, 2H, Ar-H), 7.39 (d, J = 3.8 Hz, 3H, Ar-H), 7.23 (d, J = 7.5 Hz, 2H, Ar-H), 7.13 (d, J = 7.5 Hz, 2H, Ar-H), 5.99 5.64 (m, 14H, -2, - 3), 4.94-4.84 (m, 7H, H-1), 4.52 (s, 6H, -6), 3.87 (s, 44H, H-2, H-3, H-4, H-5, H-6a, H-6b, H- 1, H-2 ), 2.91 (dd, J = 39.3, 10.7 Hz, 2H, H-6a, H-6b ), 2.30 (s, 3H, CH 3 ); 13 C NMR (150 MHz, d 6 -DMS): δ 136.4, 131.9, 129.2, 128.7, 128.5, 126.0, 123.2, 102.7, 102.6, 102.45, 102.42, 102.38, 102.0, 86.2, 85.3, 84.1, 82.1, 81.94, 81.85, 81.8, 81.5, 73.7 72.4, 60.4 60.2, 58.6, 54.3, 43.7, 21.3; IR (cm -1, KBr): 3374, 2927, 1637, 1514, 1491, 1414, 1368, 1244, 1156, 1079, 1030, 946, 860, 758, 693, 581, 527; MS (ESI): m/z 1352.7 ([M+H] + ); HRMS (ESI): Calcd. For C59H86N35 + 1352.4953, found 1352.5014. White solid; 42% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.49 7.35 (m, 5H, Ar-H), 7.25 (d, J = 8.1 Hz, 2H, Ar-H), 6.89 (d, J = 8.2 Hz, 2H, Ar-H), 5.97 (d, J = 5.7 Hz, 1H, -2 or -3), 5.87 5.73 (m, 13H, -2, -3), 4.96 4.81 (m, 7H, H-1), 4.58 (m, 6H, -6), 3.74 (s, 3H, Me), 3.71 3.31 (m, 44H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1, H-2 ), 2.98 2.86 (m, 2H, H-6a, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 158.8, 131.9, 131.1, 130.5, 129.1, 128.7, 123.2, 114.0, 102.7, 102.5, 102.42, 102.37, 102.1, 86.2, 85.4, 84.0, 82.3, 82.0, 81.9, 81.8, 81.6, 73.6 72.4, 60.4 60.2, 58.0, 55.5, 55.3, 54.2, 43.1; IR (cm -1, KBr): 3393, 2928, 1636, 1513, 1491, 1419, 1369, 1302, 1248, 1156, 1079, 1029, 946, 758, 693, 581, 528; MS (ESI): m/z 1368.5 ([M+H] + ); HRMS (ESI): Calcd. For C59H86N35 + 1368.4902, found 1368.4970. S9

White solid; 49% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.51 7.43 (m, 2H, Ar-H), 7.43 7.33 (m, 7H, Ar-H), 5.97 (d, J = 6.4 Hz, 1H, -2 or -3), 5.85 5.71 (m, 13H, -2, -3), 4.93 (d, J = 3.1 Hz, 1H, H-1), 4.86-4.83 (m, 6H, H-1), 4.56-4.46 (m, 6H, -6), 3.90 3.26 (m, 44H, H-2, H-3, H-4, H- 5, H-6a, H-6b, H-1, H-2 ), 3.03 2.82 (m, 2H, H-6a, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 138.5, 131.9, 131.1, 129.1, 128.8, 128.6, 126.0, 123.1, 102.8, 102.54, 102.47, 102.41, 102.39, 102.1, 86.0, 85.4, 84.2, 82.1, 82.0, 81.84, 81.80, 81.7, 73.6 72.4, 60.4 60.2, 58.1, 54.2, 43.7; IR (cm -1, KBr): 3373, 2928, 1637, 1491, 1410, 1368, 1336, 1245, 1156, 1079, 1029, 946, 860, 758, 694, 582, 528; MS (ESI): m/z 1372.4 ([M+H] + ); HRMS (ESI): Calcd. For C58H82ClN34 + 1372.4407, found 1372.4488. White solid; 50% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.41 (d, J = 8.7 Hz, 2H, Ar-H), 7.35-7.31 (m, 4H, Ar-H), 7.23 (t, J = 6.7 Hz, 1H, Ar-H), 6.94 (d, J = 8.8 Hz, 2H, Ar-H), 5.98 (d, J = 6.5 Hz, 1H, -2 or -3), 5.85 5.70 (m, 13H, -2, -3), 4.96 (d, J = 3.1 Hz, 1H, H-1), 4.85 (dd, J = 7.8, 3.4 S10

Hz, 6H, H-1), 4.56 4.47 (m, 6H, -6,), 3.88 3.25 (m, 47H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1, H-2, Me), 2.91 (dt, J = 14.4, 9.6 Hz, 2H, H-6a, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 159.8, 139.8, 133.6, 129.3, 128.9, 127.5, 115.4, 114.9, 103.0, 102.8, 102.7, 102.6, 102.3, 85.6, 84.4, 84.3, 82.3, 82.2, 82.14, 82.07, 82.0, 81.8, 73.9 72.7, 60.6 60.4, 58.6, 55.9, 54.3, 43.6; IR (cm -1, KBr): 3373, 2928, 1637, 1607, 1510, 1413, 1368, 1338, 1293, 1249, 1156, 1079, 1029, 946, 834, 755, 704, 580, 533; MS (ESI): m/z 1368.5 ([M+H] + ); HRMS (ESI): Calcd. For C59H86N35 + 1368.4902, found 1368.4943. White solid; 67% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.43 (d, J = 8.1 Hz, 2H, Ar-H), 7.37 7.30 (m, 6H, Ar-H), 7.24 (t, J = 6.7 Hz, 1H, Ar-H), 5.98 (d, J = 6.4 Hz, 1H, -2 or -3), 5.86 5.68 (m, 13H, -2, -3), 5.29 (t, J = 5.8 Hz, 1H, PhCH2), 4.96 (d, J = 3.0 Hz, 1H, H-1), 4.92 4.78 (m, 6H, H-1), 4.55 4.48 (m, 8H, -6, PhCH 2 ), 3.90 3.27 (m, 44H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1, H-2 ), 2.93 (dt, J = 14.5, 9.5 Hz, 2H, H-6a, H-6b ); 13 C NMR (150 MHz, d 6 -DMS): δ 143.5, 139.8, 132.0, 129.3, 128.9, 127.6, 127.2, 121.6, 103.0, 102.8, 102.7, 102.6, 102.3, 85.8, 85.6, 84.3, 82.3, 82.2, 82.1, 82.0, 81.8, 73.9 72.7, 63.2, 60.6 60.4, 58.6, 54.2, 43.6; IR (cm -1, KBr): 3373, 2927, 1636, 1508, 1413, 1368, 1246, 1205, 1156, 1079, 1029, 946, 848, 754,703, 581, 530; MS (ESI): m/z 1368.5 ([M+H] + ); HRMS (ESI): Calcd. For C59H86N35 + 1368.4902, found 1368.4938. S11

White solid; 52% yield; 1 H NMR (600 MHz, d 6 -DMS): δ 7.33 7.24 (m, 4H, Ar-H), 7.21 (t, J = 7.0 Hz, 1H, Ar-H), 5.99 (t, J = 5.8 Hz, 1H, -2 or -3), 5.83 5.68 (m, 13H, -2, -3), 4.93 (d, J = 3.3 Hz, 1H, H-1), 4.84 (dd, J = 13.8, 3.6 Hz, 6H, H-1), 4.58 4.44 (m, 6H, -6), 3.82 3.28 (m, 43H, H-2, H-3, H-4, H-5, H-6a, H-6b, H-1, H-2 ), 3.15 (d, J = 17.0 Hz, 1H, H-2 ), 2.83 (d, J = 13.2 Hz, 1H, H-6a ), 2.76 (dd, J = 13.9, 5.9 Hz, 1H, H-6b ), 1.37 1.27 (m, 1H), 0.83 0.69 (m, 2H), 0.63 0.55 (m, 2H); 13 C NMR (150 MHz, d 6 -DMS): δ 139.6, 129.0, 128.6, 127.2, 102.8, 102.6, 102.5, 102.43, 102.36, 102.0, 88.9, 84.2, 82.1, 82.0, 81.9, 81.6, 81.5, 73.7 72.2, 70.8, 60.4 60.2, 57.9, 55.4, 42.9, 31.2, 8.64, 8.61; IR (cm -1, KBr): 3374, 2929, 1636, 1409, 1369, 1331, 1250, 1203, 1156, 1032, 947, 863, 754, 701, 581, 531; MS (ESI): m/z 1302.5 ([M+H] + ); HRMS (ESI): Calcd. For C55H83N34 + 1302.4796, found 1302.4858. White solid; 26% yield; S12

1 H NMR (600 MHz, d 6 -DMS): δ 7.31 (d, J = 4.3 Hz, 4H, Ar-H), 7.26 7.20 (m, 1H, Ar-H), 6.04 (s, 1H, vinyl CH), 6.00 (d, J = 6.3 Hz, 1H, -2 or -3), 5.83-5.70 (m, 13H, -2, - 3), 4.93 4.80 (m, 7H, H-1), 4.57 4.46 (m, 6H, -6), 3.73 3.29 (m, 44H, H-2, H-3, H-4, H- 5, H-6a, H-6b, H-1, H-2 ), 2.92 (d, J = 13.4 Hz, 1H, H-6a ), 2.78 (dd, J = 13.6, 6.3 Hz, 1H, H- 6b ), 2.09 (d, J = 10.9 Hz, 4H, allyl CH 2 ), 1.58 (ddd, J = 10.9, 9.0, 5.4 Hz, 4H, -CH 2 CH 2 -); 13 C NMR (150 MHz, d 6 -DMS): δ 139.7, 134.3, 129.3, 128.8, 127.5, 120.8, 103.0, 102.8, 102,7, 102.6, 102.3, 87.3, 84.7, 83.4, 82.3, 82.1, 81.9, 81.7, 74.0 72.4, 60.6 60.4, 59.1, 55.6, 55.3, 43.9, 29.8, 25.7, 22.6, 21.8; IR (cm -1, KBr): 3382, 2927, 1637, 1419, 1369, 1243, 1156, 1079, 1029, 946, 847, 755, 704, 581, 531; MS (ESI): m/z 1342.5([M+H] + ); HRMS (ESI): Calcd. For C58H88N34 + 1342.5109, found 1342.5128. S13

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 1b S14

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 1c S15

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) of 1d S16

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2a 139.5294 131.9381 129.1018 128.7336 128.6970 127.3747 123.1762 102.8029 102.5525 102.4593 102.4211 102.1175 86.1068 85.4117 84.1717 82.0682 81.9431 81.8754 81.8068 81.6127 73.4412 73.2776 72.8847 72.5719 72.5353 72.4759 60.3810 60.2996 60.2203 58.5659 54.2860 43.4894 139.5294 131.9381 129.1018 128.7336 128.6970 127.3747 123.1762 102.8029 102.5525 102.4593 102.4211 102.1175 86.1068 82.0682 81.9431 81.8754 73.4412 72.8847 72.4759 60.3810 60.2996 60.2203 58.5659 54.2860 43.4894 S17

CSY (600 MHz, d 6 -DMS) spectrum of 2a S18

RESY (600 MHz, d 6 -DMS) spectrum (300ms) of 2a S19

RESY (600 MHz, d 6 -DMS) spectrum (600ms) of 2a S20

HSQC (600 MHz, d 6 -DMS) spectrum of 2a S21

HMBC (600 MHz, d 6 -DMS) spectrum of 2a S22

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2b 2.0000 3.1741 1.8492 1.9289 15.3622 7.5682 6.1340 65.8165 1.7369 2.8540 7.4931 7.4680 7.4613 7.3949 7.3949 7.3886 7.2317 7.2192 7.1378 7.1253 5.9587 5.8344 5.7628 5.6947 5.6535 4.9381 4.8638 4.8491 4.8354 4.5169 3.8678 2.9548 2.9325 2.8849 2.8715 2.2953 S23

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2c 5.4934 1.8682 1.8186 0.8108 14.1637 7.0000 6.3015 3.2431 2.2745 7.4613 7.4538 7.4316 7.4271 7.3936 7.3855 7.2614 7.2480 6.9014 6.8877 5.9714 5.9619 5.8621 5.8520 5.8224 5.7777 5.7559 5.7385 4.9426 4.9380 4.8517 4.8418 4.8358 4.8287 4.5992 4.5626 3.7368 3.7132 3.3238 3.3100 2.9622 2.9386 2.8928 S24

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2d S25

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2e 2.0004 4.2726 0.9351 1.9307 0.8947 13.2049 0.9900 6.0000 6.0144 69.1232 159.7561 139.7987 133.6459 129.2876 128.8731 127.5342 115.3746 114.8739 102.9909 102.7491 102.6612 102.6091 102.2971 84.4182 82.1663 82.1448 82.0168 73.6366 73.0762 72.7246 60.5898 60.5081 60.4139 58.5559 55.8832 55.8588 43.6478 2.0231 7.4153 7.4009 7.3495 7.3357 7.3237 7.3108 7.2452 7.2340 7.2228 6.9503 6.9356 5.7851 5.7723 5.7628 5.7617 5.7536 5.7222 4.8601 4.8544 4.8471 4.8414 4.5240 4.5141 3.8093 3.7870 3.7806 3.2928 2.9576 2.9354 2.9148 2.9062 2.8921 2.8823 16000 15000 14000 13000 12000 11000 10000 9000 159.7561 139.7987 133.6459 129.2876 128.8731 127.5342 115.3746 114.8739 102.9909 102.7491 102.6612 102.6091 102.2971 84.4182 82.2746 82.1663 82.1448 82.0662 82.0168 81.8008 73.6366 73.4792 73.0762 72.7246 60.5898 60.5081 60.4139 58.5559 55.8832 55.8588 54.2762 43.6478 8000 7000 6000 5000 4000 3000 2000 1000 0-1000 -2000 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 S26

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2f 2.0292 6.2843 1.0000 0.9130 14.2424 1.0137 0.9883 6.3735 8.6928 61.7493 1.8904 7.4407 7.4272 7.3528 7.3382 7.3260 7.3234 7.3139 7.2483 7.2370 7.2258 5.8009 5.7889 5.7749 5.7697 5.7653 5.7556 5.7517 5.7286 5.7172 5.2992 5.2895 5.2800 4.8553 4.8478 4.8425 4.5386 4.5264 4.5169 4.4969 3.8433 3.8222 3.7983 3.7756 3.2943 2.9659 2.9436 2.9302 2.9214 2.9065 2.8972 S27

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2g 139.6481 128.9564 128.5986 127.2411 102.7772 102.5640 102.4779 102.4270 102.3611 102.0100 88.8887 82.0728 81.9609 81.8517 81.6428 81.4903 73.4318 73.2386 72.9297 72.8327 72.5346 72.4891 60.3802 60.3176 60.2876 60.1712 57.9413 55.4035 54.0038 46.1572 42.8683 139.6481 128.9564 128.5986 127.2411 102.7772 102.5640 102.4779 102.4270 102.3611 102.0100 88.8887 82.0728 81.9609 81.8517 81.4903 73.2386 72.5346 72.4891 60.3802 60.3176 60.2876 60.1712 55.4035 46.1572 42.8683 31.1880 8.6433 8.6056-0.2603 4.0682 1.0000 0.9056 13.2675 1.0141 6.2252 6.0204 1.0777 67.7885 1.0252 0.9485 0.9067 0.9053 2.0602 2.0386 7.3097 7.2970 7.2850 7.2714 7.2593 7.2225 7.2108 5.9913 5.9810 5.8199 5.8085 5.8029 5.7999 5.7880 5.7762 5.7707 5.7638 5.7597 5.7536 5.7419 5.7338 5.7301 5.7139 5.7102 5.6971 5.6912 5.6852 5.6791 4.9302 4.9247 4.8534 4.8470 4.8301 4.8243 4.5289 4.5195 4.5099 4.5039 4.4949 3.8108 3.4301 3.3569 3.3121 3.3073 3.2910 3.2852 2.8219 2.7624 1.3219 1.3136 0.7896 0.7830 0.7787 0.7724 0.7695 0.7651 0.7595 0.6098 0.6038 0.5998 0.5958 0.5917 0.5853 S28

1 H NMR (600 MHz, d 6 -DMS) and 13 C NMR (150 MHz, d 6 -DMS) spectra of 2h 139.7436 134.2914 129.2925 128.8311 127.5191 120.7872 102.9816 102.7934 102.6593 102.5757 102.2605 83.4450 82.2550 82.1305 81.8587 73.6406 73.0769 72.7232 60.5591 60.4927 60.3719 59.0884 55.5925 55.2827 43.9201 29.7903 25.7241 22.5892 21.8355 75000 70000 65000 60000 55000 50000 45000 40000 139.7436 134.2914 129.2925 128.8311 127.5191 120.7872 102.9816 102.7934 102.6593 102.5757 102.2605 87.3225 84.6761 83.4450 82.2550 82.1305 81.8587 81.6574 73.7244 73.6406 73.1632 73.0769 72.7232 72.6463 60.5591 60.4927 60.3719 59.0884 55.5925 55.2827 43.9201 35000 30000 25000 20000 15000 10000 5000 0-5000 -10000 210 200 190 180 170 160 150 140 130 120 110 100 f1 (ppm) 90 80 70 60 50 40 30 20 10 0 S29