Total Synthesis of Biselyngbyolide A Yurika Tanabe, Eisuke Sato, Naoya Nakajima, Akifumi Ohkubo, Osamu Ohno, and Kiyotake Suenaga

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1 Total Synthesis of Biselyngbyolide A Yurika Tanabe, Eisuke Sato, Naoya Nakajima, Akifumi Ohkubo, Osamu Ohno, and Kiyotake Suenaga Supporting Information Experimental details including spectral data S2 ~ S20 Determination of stereochemistry of alcohol 21 and epi-21 S21 1H NMR spectra of all new compounds S22 ~ S52 13C NMR spectra of all new compounds S53 ~ S80 S1

2 Experimental Procedures and Spectral Data for All New Compounds. General Methods. Chemicals and solvents were the best grade available and were used as received from commercial sources. Optical rotations were measured with a JASCO DIP-360 polarimeter. 1 H NMR spectra were recorded on a JEOL JNM-EX270 (270 MHz) a JEOL JNM-A400 (400 MHz), or a JEOL JNM-GX400 (400 MHz) instrument. Chemical shifts are reported values in parts per million relative to the residual solvent signal (CHD2OD: = 3.31 ppm; CHCl3: = 7.26 ppm; CHD5: = 7.16 ppm for 1 H) and coupling constants are in hertz (Hz). The following abbreviations are used for spin multiplicity: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, and br = broad. 13 C NMR spectra were recorded on a JEOL JNM-EX270 (67.8 MHz) a JEOL A-GX400 (100.4 MHz), or a JEOL JNM-GX400 (100.4 MHz) instrument using CD3OD and CDCl3 as a solvent, respectively. Chemical shifts are reported in parts per million from the solvent signal (CDCl3: = 77.2 ppm; CHD2OD: = 49.0 ppm). IR spectra were recorded on a JASCO FT/IR-410 instrument and are reported in wavenumbers (cm -1 ). ESI mass spectra were recorded on a LCT premier EX spectrometer (Waters). Both TLC analysis and preparative TLC were conducted on E. Merck precoated silical gel 60 F254. Fuji Silysia silica gel BW-820 MH and FL-60D were used for column chromatography unless otherwise noted. Organic solvents for moisture-sensitive reactions were distilled from the following drying agents: THF (Na-benzophenone ketyl), diethyl ether (Na-benzophenone ketyl), benzene (Na), toluene (Na), CH2Cl2 (P2O5), DMSO (calcium hydride). Anhydrous DMF was used as obtained from commercial supplies. All moisture-sensitive reactions were performed under an atmosphere of nitrogen, and the starting materials were azeotropically dried with benzene before use. Alcohol 25: To a stirred suspension of lithium acetylide ethylenediamine complex (2.78 g, 30.2 mmol) in DMSO (7.6 ml) was added a solution of (R)-(+)-trityl glycidyl ether (10) (3.79 g, 12.0 mmol) in THF (9.0 ml) at room temperature. After stirring for 1 h, the mixture was diluted with saturated aqueous NH4Cl at 0 C, and extracted with EtOAc (3 50 ml). The combined extracts were washed with brine (70 ml), dried (Na2SO4), filtered, and concentrated. Crude alcohol 25 (4.60 g) was used for the next reaction without further purification. S2

3 Sylil ether 26: To a stirred solution of crude alcohol 25 (4.60 g) in DMF (15 ml) were added imidazole (3.68 g, 54.0 mmol) and TBDPSCl (6.0 ml, 23.3 mmol) at room temperature. After stirring for 40 min, the mixture was diluted with cooled H2O (30 ml), and extracted with EtOAc (3 50 ml). The combined extracts were washed with brine (70 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (150 g, hexane-etoac 25:1) to give silyl ether 26 (4.54 g, 99% in 2 steps) as a yellow oil: [ ]D (c 1.26, CHCl3); IR (neat, cm -1 ) 3308, 3069, 2931, 2858, 1590, 1490, 1448, 1428, 1362, 1218, 1112, 998, 936, 822, 760, 700, 633; 1H NMR (400 MHz, CDCl3) 7.70 (m, 2H), 7.62 (m, 2H), (m, 21H), 4.01 (dtd, J = 6.4, 5.1, 4.9 Hz, 1H), 3.28 (d, J = 5.1 Hz, 2H), 2.57 (ddd, J =16.7, 6.4, 2.6 Hz, 1H), 2.46 (ddd, J =16.7, 4.9, 2.8 Hz, 1H), 1.88 (dd, J = 2.8, 2.6 Hz, 1H), 1.09 (s, 9H); 13 C NMR (100 MHz, CDCl3) 144.1, 136.1, 135.9, 133.9, 129.8, 129.7, 128.9, 127.8, 127.7, 127.7, 127.0, 86.7, 81.1, 71.1, 70.1, 66.1, 27.1, 24.4, 19.4; HRMS (ESI) m/z , calcd for C40H41O2Si [M+H] Alcohol 11: To a stirred solution of silyl ether 26 (5.59 g, 9.67 mmol) in CH2Cl2 (6 ml) and MeOH (6 ml) was added TsOH H2O (183 mg, mmol) at room temperature. After stirring for 2.5 h, the mixture was diluted with saturated aqueous NaHCO3 (30 ml), extracted with EtOAc (3 50 ml). The combined extracts were washed with brine (50 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (140 g, hexane-etoac 30:1 to 10:1) to give alcohol 11 (2.78 g, 85%) as a colorless oil: [ ]D (c 1.07, CHCl3); IR (neat, cm -1 ) 3429, 3307, 3072, 2932, 2858, 1473, 1428, 1363, 1240, 1104, 1045, 977, 937, 822, 739, 612; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 3.94 (ddt, J = 8.4, 4.6, 4.5 Hz, 1H), 3.67 (d, J =4.6 Hz, 2H), 2.45 (ddd, J = 16.7, 8.4, 2.6 Hz, 1H), 2.29 (ddd, J = 16.7, 4.5, 2.6 Hz, 1H), 1.93 (t, J = 2.6 Hz, 1H), 1.09 (s, 9H); 13 C NMR (100 MHz, CDCl3) 135.9, 135.7, 133.5, 133.4, 130.0, 127.9, 127.8, 80.5, 72.0, 70.5, 65.3, 27.0, 23.5, 19.4; HRMS (ESI) m/z , calcd for C21H27O2Si [M+H] S3

4 Aldehyde 27: To a stirred solution of alcohol 11 (2.78 g, 8.23 mmol) in CH2Cl2 (40 ml) was added Dess-Martin periodinane (3.86 g, 9.14 mmol) at room temperature. The mixture was stirred for 25 min, diluted with saturated aqueous Na2S2O3 (30 ml), and extracted with EtOAc (3 50 ml). The combined extracts were washed with saturated aqueous NaHCO3 (50 ml) and brine (50 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (75 g, hexane-etoac 20:1) to give aldehyde 27 (2.67 g, 96%) as a colorless oil: [ ]D (c 1.48, CHCl3); IR (neat, cm -1 ) 3302, 3073, 3049, 2956, 2931, 2859, 1738, 1470, 1427, 1112, 822, 740, 701, 612; 1 H NMR (400 MHz, CDCl3) 9.64 (d, J = 1.0 Hz, 1H), (m, 4H), (m, 6H), 4.11 (ddd, J = 6.3, 5.9, 1.0 Hz, 1H), 2.51 (ddd, J = 17.1, 6.3, 2.9 Hz, 1H), 2.48 (ddd, J =17.1, 5.9, 2.9 Hz, 1H) 1.99 (t, J = 2.9 Hz, 1H), 1.13 (s, 9H); 13 C NMR (100 MHz, CDCl3) 202.1, 135.9, 135.9, 132.8, 132.7, 130.3, 130.0, 128.1, 128.0, 78.9, 75.8, 71.2, 27.0, 23.2, 19.5; HRMS (ESI) m/z , calcd for C21H25O2Si [M+H] Conjugated ester 12: To a stirred solution of Ando s reagent (2.43 g, 6.71 mmol) in THF (4 ml) was added NaH (60% in oil, 300 mg, 7.50 mmol) at 0 C. After stirring for 30 min, a solution of aldehyde 27 (2.05 g, 6.09 mmol) in THF (6 ml) was added to the reaction mixture at -78 C. The mixture was warmed to 0 C and stirred for 2.5 h. The mixture was diluted with saturated aqueous NH4Cl (20 ml) and extracted with EtOAc (3 30 ml). The combined extracts were washed with H2O (10 ml) and brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (70 g, hexane-etoac 20:1) to give conjugated ester 12 (2.38 g, 93%) as a colorless oil: [ ]D (c 1.03, CHCl3); IR (neat, cm -1 ) 3308, 3072, 2961, 2932, 2858, 1713, 1427, 1206, 1112, 1075, 739, 701, 611; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 5.97 (dq, J = 8.3, 1.5 Hz, 1H), 5.20(dt, J = 8.3, 4.9 Hz, 1H), 3.94 (q, J = 6.4 Hz, 2H), 2.44 (dd, J = 4.9, 2.4 Hz, 2H), 1.95 (t, J = 2.4 Hz, 1H), 1.73 (d, J = 1.5 Hz, 3H), 1.55 (t, J =6.4 Hz, 3H), 1.07 (s, 9H); 13 C NMR (100 MHz, CDCl3) 167.0, 144.2, 136.0, 134.1, 133.9, 129.8, 129.7, 127.6, 127.6, 127.1, 81.1, 70.0, 68.8, 60.4, S4

5 27.7, 27.1, 20.3, 19.5, 14.1; HRMS (ESI) m/z , calcd for C26H33O3Si [M+H] Allylic alcohol 28: To a stirred solution of conjugated ester 12 (2.38 g, 5.66 mmol) in THF (10 ml) was added lithium alminium hydride (1.0 M solution in THF, 13.5 ml, 13.5 mmol) at -25 C. After stirring for 15 min at -25 C, the mixture was diluted with saturated aqueous Na/K tartrate (20 ml) and stirred for additional 4 h at room temperature. The reaction mixture was extracted with EtOAc (3 20 ml). The combined extracts were washed with brine (20 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (75 g, hexane-etoac 20:1) to give allylic alcohol 28 (1.91 g, 89%) as a colorless oil: [ ]D (c 1.06, CHCl3); IR (neat, cm -1 ) 3417, 3307, 3071, 3050, 2932, 2858, 1473, 1427, 1112, 1072, 1005, 937, 823, 740, 702, 614; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 5.27 (d, J = 8.9 Hz, 1H), 4.55 (ddd, J = 8.9, 8.3, 4.9 Hz, 1H), 3.53 (d, J = 5.9 Hz,2H), 2.52 (ddd, J = 16.6, 4.9, 2.9 Hz, 1H), 2.38 (ddd, J = 16.6, 8.3, 2.9 Hz, 1H), 1.94 (t, J = 2.9 Hz, 1H), 1.64 (s, 3H), 1.05 (s, 9H); 13 C NMR (100 MHz, CDCl3) 136.8, 136.1, 136.0, 134.0, 133.8, 130.0, 129.9, 129.6, 127.8, 127.6, 81.7, 70.1, 68.3, 61.5, 28.5, 27.0, 21.1, 19.4; HRMS (ESI)m/z , calcd for C24H31O2Si [M+H] Allylicbromide 13: To a stirred solution of allylic alcohol 28 (385 mg, 1.02 mmol) in CH2Cl2 (3.8 ml) were added triphenyl phosphine (401 mg, 1.53 mmol) and carbon tetrabromide (507 mg, 1.53 mmol) at 0 C. The mixture was stirred for 30 min, and concentrated. The residual mixture was purified by column chromatography on silica gel (15 g, hexane-etoac 20:1) to give allylic bromide 13 (449 mg, quant.) as a colorless oil: [ ]D (c 1.05, CHCl3); IR (neat, cm -1 ) 3306, 3071, 2932, 2858, 1473, 1427, 1207, 1112, 1072, 740, 701, 668, 644, 613; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 5.42 (dq, J = 9.3, 1.4 Hz, 1H), 4.53 (ddd, J = 9.3, 6.3, 4.9 Hz, 1H), 3.47 (d, J = 10.2 Hz, 1H), 3.36 (d, J = 10.2 Hz, 1H), 2.43 (ddd, J = 16.0, 4.9, 2.4 Hz, 1H), 2.39 S5

6 (ddd, J = 16.0, 6.3, 2.4 Hz, 1H), 1.95 (t, J = 2.4 Hz, 1H), 1.71 (d, J = 1.4 Hz, 3H), 1.05 (s, 9H); 13 C NMR (100 MHz, CDCl3) 136.1, 136.0, 133.8, 133.7, 133.0, 132.2, 130.0, 129.8, 127.8, 127.7, 80.8, 70.5, 68.3, 31.5, 28.1, 27.0, 22.0, 19.4; HRMS (ESI) m/z , calcd for C24H30BrOSi [M+H] Diene 14: To a stirred degassed solution of allylic bromide 13 in THF (537mg, 1.09 mmol) were added trans-1-propen-1-ylbornic acid (227 mg, 2.65 mmol), K3PO4 (554 mg, 2.61 mmol), Pd(dba)2 (58.3 mg, 0.10 mmol) at room temperature. After stirring for 1.5 h, the reaction mixture was diluted with H2O (10 ml) and Et2O (5 ml), and extracted with Et2O (3 10 ml). The combined extracts were washed with 0.5 M aqueous NaOH (10 ml) and brine (20 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (50 g, hexane-toluene 50:1 to 20:1 to 10:1) to give a geometric mixture of diene 14 (229 mg, 52%, 18E/18Z = ca 2:1) as a colorless oil: IR (neat, cm -1 ) 3310, 3071, 2962, 2932, 2857, 1472, 1428, 1112, 1069, 937, 823, 739, 701, 613; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 5.36 (m, 0.3H), 5.27 (m, 1H), 5.24 (m, 0.3H), 5.19 (m,0.7h), 5.02 (m, 0.7H), 4.55 (m, 1H), 2.49 (m, 0.6H), 2.45 (m, 0.3 H), 2.41 (m,0.3h), 2.35 (m, 1.4 H), 2.31 (dd, J = 14.6, 6.5 Hz, 0.7H), 2.16 (dd, J =14.6, 6.7 Hz, 0.7H), 1.92 (t, J =2.7 Hz, 0.7H), 1.90 (t, J =2.5 Hz, 0.3H), 1.65 (dd, J =6.1, 1.1 Hz, 2.1H), 1.54 (d, J =1.1 Hz, 0.9H), 1.53 (dd, J =8.8, 1.4 Hz, 0.9H), 1.14 (d, J = 1.1 Hz, 2.1H), 1.06 (s, 9H); 13 C NMR (100 MHz, CDCl3) 136.6, 136.1, 136.1, 134.4, 134.3, 134.2, 129.7, 129.7, 129.6, 129.5, 128.7, 128.3, 127.7, 127.6, 127.4, 127.2, 126.7, 126.2, 81.7, 81.6, 69.8, 69.6, 69.0, 68.5, 42.7, 35.6, 28.8, 28.5, 27.1, 23.2, 19.4, 18.0, 17.9, 16.6; HRMS (ESI) m/z , calcd for C27H35OSi [M+H] Vinyl stannane 15: To a stirred degassed solution of diene 14 (49.4 mg, mmol) in toluene (0.6 ml) were added tri-n-butyltin hydride (0.16 ml, mmol) and AIBN (6.4mg, 39.0 mol) at 80 C, and the reaction mixture was stirred at 80 C for 2 h. After cooled to room temperature, the mixture was concentrated. The residual oil was S6

7 purified by column chromatography on silica gel (15 g, hexane-toluene 100:1 to 50:1) to give vinyl stannane 15 (61.3 mg, 72%, 18E/18Z = ca 2:1) as a colorless oil: 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 5.87 (m, 1H), 5.19 (m, 1H), 5.18 (m, 1H), (m, 2H), 4.43 (m, 1H), (m, 6H), 2.45 (m, 1H), 2.11 (m, 1H), 1.52 (dd, J = 6.7, 1.1 Hz, 3H), (m, 6H), 1.48 (d, J =1.4 Hz, 3H), (m, 12H), 1.03 (s, 9H), 0.88 (t, J = 7.2 Hz, 9H); HRMS (ESI) m/z , calcd for C39H63OSiSn [M+H] Alcohol 4: To a stirred solution of vinyl stannane 15 (39.0 mg, 56.2 mol) in THF (0.1 ml) was added tetrabutylammonium fluoride (TBAF) (1.0 M solution in THF, 0.09 ml, 90 mol) at 60 C. After stirring for 5 h, the mixture was diluted with saturated aqueous NH4Cl (2 ml), and extracted with EtOAc (3 3 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (13 g, hexane-etoac 20:1) to give crude alcohol 4 (32.1 mg, mixture with TBDPSF) as a colorless oil. Dibromoolefine 29: To a stirred solution of triphenylphosphine (3.21 g, 12.2 mmol) and carbon tetrabromide (2.03 g, 6.12 mmol) in CH2Cl2 (8 ml) were added a solution of aldehyde 16 (588 mg, 3.06 mmol) in CH2Cl2 (2 ml) and 2,6-lutidine (0.76 ml, 6.56 mmol) at 0 C. After stirring for 1 h, the mixture was diluted with saturated aqueous NH4Cl (10 ml) and extracted with hexane (3 15 ml). The combined extracts were washed with saturated aqueous Na2S2O3 (10 ml) and brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (30 g, hexane-etoac 15:1) to give dibromoolefin 29 (1.03 g, 97%) as a colorless oil: [ ]D (c 1.05, CHCl3); IR (neat, cm -1 ) 2962, 2928, 2868, 1454, 1363, 1104, 766, 735, 697; 1 H NMR (400 MHz, CDCl3) (m, 5H), 6.21 (d, J = 9.3 Hz, 1H), 4.50 (s, 2H), 3.48 (m, 2H), 2.68 (m, 1H), 1.70 (m, 1H), 1.62 (m, 1H), 1.03 (d, J = 3.8 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 143.8, 138.5, 128.5, 127.8, 127.7, 87.9, 73.3, 68.2, 36.1, 35.7, S7

8 19.4; HRMS (ESI) m/z , calcd for C13H16OBr2Na [M+Na] Alkyne 17: To a stirred solution of dibromoolefin 29 (789 mg, 2.27 mmol) in THF (2.4 ml) were added n-buli (1.6 M solution in hexane, 3.1 ml, 4.96 mmol) and iodomethane (0.55 ml, 8.83 mmol) at -78 C, and the mixture was stirred at room temperature for 2 h. The mixture was diluted with H2O (5 ml) and extracted with EtOAc (3 10 ml). The combined extracts were washed with H2O (10 ml) and brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (12 g, hexane-etoac 15:1) to give alkyne 17 (442 mg, 96%) as a yellow oil: [ ]D (c 1.00, CHCl3); IR (neat, cm -1 ) 2966, 2918, 2859, 1454, 1364, 1103, 737, 698; 1 H NMR (400 MHz, CDCl3) (m, 5H), 4.52 (s, 2H), 3.60 (m, 2H), 2.60 (m, 2H), 1.77, (d, J = 2.4 Hz, 3H), 1.72 (m, 1H), 1.70 (m, 1H), 1.15 (d, J = 6.3 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 138.8, 128.5, 127.8, 127.6, 83.3, 76.0, 73.1, 68.5, 37.3, 23.0, 21.6, 3.6; HRMS (ESI) m/z , calcd for C14H19O [M+H] Vinyl iodide 6: To a suspension of Schwartz s reagent (513 mg, 1.99 mmol) in benzene (2 ml) was added a solution of alkyne 17 (201 mg, mmol) in benzene (0.7 ml) in the dark at 55 C. After stirring for 1.5 h at same temperature, iodine (600 mg, 2.36 mmol) was added to the reaction mixure, and the mixture was stirred for 1 h. The mixture was cooled to room temperature, diluted withh2o (2 ml) and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated aqueous Na2S2O3 (5 ml) and brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (13 g, hexane-etoac 20:1) to give vinyl iodide 6 (297 mg, 90%) as a colorless oil: [ ]D (c 1.08, CHCl3); IR (neat, cm -1 ) 2957, 2925, 2867, 1633, 1496, 1454, 1378, 1363, 1152, 1104, 1051, 1028, 735, 698; 1 H NMR (400 MHz, CDCl3) (m, 5H), 5.92 (dq, J = 10.2, 2.4 Hz, 1H), 4.47 (s, 2H), 3.44 (m, 2H), 2.64 (m, 1H), 2.37 (d, J = 2.4 Hz, 3H), 1.66 (m, 1H), 1.48 (m, 1H), 0.97 (d, J = 5.8 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 146.7, 138.6, 128.5, 127.8, 127.7, 93.4, 73.2, S8

9 68.3, 36.8, 32.6, 27.9, 20.6; HRMS (ESI) m/z , calcd for C14H20IO [M+H] PMB ether 30: To a stirred solution of freshly prepared 4-methoxybenzyl trichloroacetimidate (5.5 g, 19.6 mmol) in CH2Cl2 (18 ml) were added a solution of allyl alcohol 18 (4.75 g, 13.4 mmol) in CH2Cl2 (12 ml) and (±)-camphor-10-sulfonic acid (311 mg, 1.34 mmol) at room temperature. After stirring for 23 h, the mixture was diluted with saturated aqueous NaHCO3 (20 ml), and extracted with EtOAc (3 50 ml). The combined extracts were washed with brine (20 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (200 g, hexane-etoac 20:1) to give PMB ether 30 (4.71 g, 74%) as a colorless oil: [ ]D (c 1.03, CHCl3); IR (neat, cm -1 ) 2954, 2931, 2857, 1613, 1514, 1428, 1248, 1112, 1089, 823, 738, 703; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 7.20 (d, J = 8.8 Hz, 2H), 6.84 (d, J = 8.8 Hz, 2H), 5.84 (ddt, J = 18.0, 8.8, 7.0 Hz, 1H), 5.08 (d, J = 18.0 Hz), 5.06 (d, J = 8.8 Hz), 4.49 (d, J = 11.0 Hz, 1H), 4.38 (d, J = 11.0 Hz, 1H), 3.83 (m, 1H), 3.79 (s, 3H), 3.73 (m, 2H), 2.32 (dd, J = 7.0, 5.8 Hz, 2H), 1.77 (q, J = 6.3 Hz, 2H), 1.05 (s, 9H); 13 C NMR (100 MHz, CDCl3) 159.2, 135.7, 135.1, 134.1, 131.1, 129.7, 129.4, 127.8, 117.1, 113.9, 75.2, 71.0, 60.7, 55.4, 38.7, 37.1, 27.0, 19.3; HRMS (ESI) m/z , calcd for C30H39O3Si [M+H] Aldehyde 19: To a stirred solution of PMB ether 30 (4.50 g, 9.48 mmol) in acetone/h2o (3:1, v/v, 48 ml) were added NMO (3.33 g, 28.4 mmol) and OsO4 (0.5 M solution in THF, 0.8 ml, 0.4 mmol) at room temperature, and the resultant mixture was stirred at room temperature for 2 h. To the mixture was added NaIO4 (4.46 g, 20.9 mmol), and the reaction mixture was stirred at room temperature for 30 min. The mixture was diluted with saturated aqueous Na2S2O3 (10 ml), and extracted with EtOAc (3 20 ml). The combined extracts were washed with saturated aqueous Na2S2O3 (15mL), brine (15 ml), dried (Na2SO4), filtered, and concentrated. The residual S9

10 oil was purified by column chromatography on silica gel (90 g, hexane-etoac 10:1 to 4:1) to give aldehyde 19 (3.52 g, 78%) as a colorless oil: [ ]D (c 1.05, CHCl3); IR (neat, cm -1 ) 2956, 2932, 2857, 2727, 1724, 1513, 1249, 1112, 1036, 823, 703; 1 H NMR (400 MHz, CDCl3) 9.73 (dd, J = 2.5, 2.0 Hz, 1H), (m, 4H), (m, 6H), 7.18 (d, J = 8.5 Hz, 2H), 6.84 (d, J = 8.5 Hz, 2H), 4.44 (s, 2H), 4.18 (m, 1H), 3.83 (m, 1H), 3.79 (s, 3H), 3.75 (m, 1H), 2.64 (ddd, J = 16.4, 7.2, 2.5 Hz, 1H), 2.57 (ddd, J = 16.4, 4.9, 2.0 Hz, 1H), 1.91 (m, 1H), 1.78 (m, 1H), 1.06 (s, 9H); 13 C NMR (100 MHz, CDCl3) 201.8, 159.4, 135.7, 133.7, 130.4, 129.9, 129.6, 127.9, 114.0, 71.4, 71.3, 60.2, 55.4, 48.7, 37.3, 27.0, 19.3; HRMS (ESI) m/z , calcd for C29H36O4SiNa [M+Na] Alcohol 20: To a stirred solution of (+)-B-methoxy(diisopinocamphenyl)borane (2.30 g, 7.27 mmol) in Et2O (15 ml) was added allylmagnesium bromide (1.0 M solution in Et2O, 6.4 ml, 6.4 mmol)at 0 C dropwise over 10 min. After 5 min, the reaction mixture was allowed to stirr at room temperature for 75 min. The mixture was cooled to -78 C, and a solution of aldehyde 19 (1.90 g, 3.99 mmol) in Et2O (22 ml) was added dropwise over 1 h. The reaction mixture was sttired at -78 C for 2 h and then stirred at room temperature for 14 h. The reaction mixture was diluted with 30% aqueous H2O2 (4 ml) and 3 M aqueous NaOH (8 ml), stirred at room temperature for 4 h, and extracted with EtOAc (3 15 ml). The combined extracts were washed with brine (15 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (110 g, hexane-etoac 25:1 to 5:1) to give alcohol 20 (1.85 g, 89%) as a colorless oil: [ ]D (c 1.06, CHCl3); IR (neat, cm -1 ) 3476, 2931, 2858, 1513, 1248, 1112, 1088, 1036, 823, 738, 702; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 6H), 7.21 (d, J = 8.8 Hz, 2H), 6.86 (d, J = 8.8 Hz, 2H), 5.83 (ddt, J = 16.6, 10.6, 6.5 Hz, 1H), 5.10 (d, J = 16.6 Hz, 1H), 5.01 (d, J = 10.6 Hz, 1H), 4.52 (d, J = 11.0 Hz, 1H), 4.36 (d, J = 11.0 Hz, 1H), (m, 4H), 3.80 (s, 3H), 2.19 (q, J = 6.5 Hz, 2H), 1.96 (m, 1H), 1.77 (m, 1H), 1.64 (m, 2H), 1.08 (s, 9H); 13 C NMR (100 MHz, CDCl3) 159.4, 135.7, 135.1, 133.8, 130.1, 129.8, 129.7, 127.8, 117.4, 114.0, 71.0, 70.6, 60.4, 55.4, 42.2, 40.8, 36.7, 27.0, 19.3; HRMS (ESI) m/z , calcd for C32H42O4SiNa [M+Na] S10

11 PMP acetal 31: To a stirred solution of alcohol 20 (173 mg, mmol) in CH2Cl2 (1.4 ml) were added MS3A (183 mg) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (92.2 mg, mmol) at 0 C. After stirring for 20 min at room temperature, the reaction mixture was diluted with saturated aqueous NaHCO3 (5 ml) and EtOAc (5mL), and stirred for additional 20 min. The reaction mixture was extracted with EtOAc (3 10 ml). The combined extracts were washed with saturated aqueous Na2S2O3 (10 ml), brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (11 g, hexane-etoac 10:1) to give PMP acetal 31 (143 mg, 83%) as a colorless oil: [ ]D (c 1.00, CHCl3); IR (neat, cm -1 ) 2931, 2857, 1616, 1517, 1428, 1249, 1112, 1011, 739, 702; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 8H), 6.88 (d, J = 9.0 Hz, 2H), 5.89 (ddt, J = 17.1, 9.9, 6.5 Hz, 1H), 5.47 (s, 2H), 5.13 (d, J = 17.1 Hz, 1H), 5.09 (d, J = 9.9 Hz, 1H), 4.07 (m, 1H), 3.92 (m, 1H), 3.86 (m, 1H), 3.79 (s, 3H), 3.77 (m, 1H), 2.46 (dt, J = 14.1, 6.5 Hz, 1H), 2.28 (dt, J = 14.1, 6.5 Hz, 1H), 1.87 (m, 1H), 1.82 (m, 1H), 1.61 (dt, J = 13.0, 2.5 Hz, 1H), 1.40 (dt, J = 13.0, 11.2 Hz, 1H), 1.06 (s, 9H); 13 C NMR (100 MHz, CDCl3) 159.9, 135.7, 134.3, 134.0, 133.9, 131.6, 129.7, 129.7, 127.8, 127.5, 117.4, 113.6, 100.6, 76.4, 73.6, 59.8, 55.5, 40.5, 38.9, 36.7, 27.0, 19.4; HRMS (ESI) m/z , calcd for C32H41O4Si [M+H] Aldehyde 7: To a stirred solution of PMP acetal 31 (134 mg, mmol) in acetone/h2o (3:1, v/v, 4 ml) were added NMO (92 mg, mmol) and OsO4 (0.5 M solution in THF, 0.04 ml, 0.02 mmol) at room temperature, and the resultant mixture was stirred at room temperature for 2 h. To the mixture was added NaIO4 (163 mg, 0.76 S11

12 mmol), and the reaction mixture was stirred at room temperature for 30 min. The mixture was diluted with saturated aqueous Na2S2O3 (5 ml), and extracted with EtOAc (3 10 ml). The combined extracts were washed with saturated aqueous Na2S2O3 (10 ml), brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (13 g, hexane-etoac 5:1 to 3:1) to give aldehyde 7 (129 mg, 96%) as a colorless oil: [ ]D (c 1.05, CHCl3); IR (neat, cm -1 ) 2960, 2931, 2857, 2735, 1727, 1615, 1518, 1428, 1250, 1112, 1034, 826, 741, 703; 1 H NMR (400 MHz, CDCl3) 9.86 (dd, J = 2.0, 1.6 Hz, 1H), (m, 4H), (m, 8H), 6.88 (d, J = 8.8 Hz, 2H), 5.52 (s, 1H), 4.34 (m, 1H), 4.14 (m, 1H), 3.92 (m, 1H), 3.81 (s, 3H), 3.77 (m, 1H), 2.79 (ddd, J = 16.8, 7.2, 2.0 Hz, 1H), 2.58 (ddd, J = 16.8, 4.9, 1.6 Hz, 1H), 1.95 (m, 1H), 1.87 (m, 1H), 1.66 (dt, J = 13.0, 2.5 Hz, 1H), 1.48 (dt, J = 13.0, 11.2 Hz, 1H), 1.07 (s, 9H); 13 C NMR (100 MHz, CDCl3) 200.7, 160.0, 135.7, 133.9, 133.9, 131.0, 129.8, 129.7, 127.8, 127.8, 127.5, 113.7, 100.7, 73.4, 72.0, 59.6, 55.4, 49.5, 38.7, 36.9, 27.0, 19.4; HRMS (ESI) m/z , calcd for C31H38O5SiNa [M+Na] Allylic alcohol 21: To a stirreddegassed solution of aldehyde 7 (387 mg, mmol) and vinyl iodide 7 (669 mg, 2.03 mmol) in DMSO (4.4 ml) were added a mixture of CrCl2 (1.73 g, 14.1 mmol) and NiCl2 (22.2 mg, mmol) at room temperature, and the mixture was stirred for 16 h at room temperature. The reaction mixture was diluted with saturated aqueous NH4Cl (5 ml)and extracted with EtOAc (5 10 ml). The combined extracts were washed with saturated aqueous NaHCO3 (10 ml), brine (10 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (17 g, hexane-etoac 10:1 to 8:1) to give allyl alcohol 21 (196 mg, 36%) and a mixture of allylic alcohol 21 and epi-21 (247 mg, 21 : epi-21 = 3:5, 46%) as a colorless oil: [ ]D (c 1.04, CHCl3); IR (neat, cm -1 ) 3488, 2953, 2929, 2858, 1614, 1518, 1429, 1250, 1112, 1035, 1010, 825, 739, 702; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 13H), 6.88 (d, J = 8.5 Hz, 2H), 5.49 (s, 1H), 5.22 (d, J = 9.4 Hz, 1H), 4.47 (s, 2H), 4.29 (dd, J = 8.9, 3.1 Hz, 1H), 4.10 (m, 1H), 4.02 (m, 1H), 3.93 (m, 1H), 3.81 (s, 3H), 3.79 (m, 1H), 3.43 (m, 2H), 2.61 (m, 1H), (m, 2H), 1.82 (m, 1H), 1.68 (m, 1H), 1.64 (s, 3H), (m, 4H), 1.07 (s, 9H), 0.98 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.9, 138.7, 135.9, 135.7, 134.0, 133.9, 132.1, S12

13 131.1, 129.8, 129.7, 128.5, 127.8, 127.6, 127.4, 113.7, 100.6, 77.4, 76.6, 73.5, 73.1, 68.8, 59.7, 55.4, 41.5, 38.8, 37.4, 37.3, 28.9, 27.0, 21.2, 19.4, 11.9; HRMS (ESI)m/z , calcd for C45H58O6SiNa [M+Na] epi-21: Analytical sample of epi-21 could be purified by PLC (hexane-etoac 4:1). [ ]D (c 0.75, CHCl3); IR (neat, cm -1 ) 3484, 2954, 2929, 2858, 1614, 1517, 1428, 1250, 1171, 1112, 1035, 825, 738, 702; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 13H), 6.87 (d, J = 8.8 Hz, 2H), 5.45 (s, 1H), 5.22 (dq, J = 9.4, 0.9 Hz, 1H), 4.49 (d, J = 11.9 Hz, 1H), 4.45 (d, J = 11.9 Hz, 1H), 4.29 (dd, J = 7.2, 3.1 Hz, 1H), (m, 2H), 3.91 (m, 1H), 3.81 (s, 3H), 3.79 (m, 1H), 3.44 (m, 2H), 2.60 (m, 1H), (m, 2H), 1.76 (m, 2H), 1.69 (m, 1H), 1.62 (d, J = 0.9 Hz, 3H), (m, 3H), 1.05 (s, 9H), 0.94 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.9, 138.7, 136.4, 135.7, 134.0, 131.4, 131.4, 129.7, 128.5, 127.8, 127.8, 127.8, 127.7, 127.5, 113.7, 100.6, 77.5, 74.4, 73.5, 73.1, 68.7, 59.7, 55.5, 40.9, 38.9, 37.5, 37.1, 28.9, 27.0, 21.2, 19.4, 12.5; HRMS (ESI)m/z , calcd for C45H58O6SiNa [M+Na] Conjugated ketone 32: To a stirred solution of a mixture of allyl alcohol 21 and epi-21 (247mg, mmol) in CH2Cl2 (2 ml) was added Dess-Martin periodinane (290mg, mmol) at room temperature. The mixture was stirred for 1 h, diluted with saturated aqueous Na2S2O3 (2 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated aqueous NaHCO3 (5 ml) and brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (14 g, hexane-etoac 8:1) to give conjugated ketone 32 (250 mg, quant.) as a colorless oil: [ ]D (c 1.02, CHCl3); IR (neat, cm -1 ) 2959, 2930, 2858, 1666, 1618, 1518, 1428, 1249, 1171, 1112, 1034, 825, 739, 703; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 13H), 6.87 (d, J = 8.8 Hz, 2H), 6.44 (dq, J = 9.9, 1.1 Hz, 1H), 5.51 (s, 1H), 4.43 (s, 2H), 4.39 (m, 1H), 4.14 (m, 1H), 3.93 (m, 1H), 3.80 (m, 1H), 3.79 (s, 3H), 3.41 (m, 1H), 3.33 (m, 1H), 3.17 (dd, J = 16.2, 6.3 Hz, 1H), 2.84 (m, 1H), 2.72 (dd, J = 16.2, 6.3 Hz, 1H), (m, 2H), 1.83 (d, J = 1.1 Hz, 3H), 1.77 (m, 2H), 1.56 (m, 1H), 1.43 (q, J = 11.2 Hz, 1H), 1.08 (s, 9H), 1.05 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 199.7, 159.8, 148.8, 138.4, 136.8, 135.7, 134.0, 133.9, 131.4, 129.7, 129.7, 128.5, 127.8, 127.7, 127.5, 113.6, 100.6, 73.9, 73.3, 73.2, 68.2, 59.7, 55.4, 43.6, 38.8, S13

14 37.3, 36.8, 30.7, 27.0, 20.2, 19.3, 11.5; HRMS (ESI) m/z , calcd for C45H56O6SiNa [M+Na] Allylic alcohol 21: To a stirred solution of ketone 32 (183 mg, mmol) in toluene (0.5 ml) were added (R)-(+)-2-methyl-CBS-oxazaborolidine (22) (13 mg, 46.9 mol) and BH3 SMe2 (0.06 ml, 1.02 mmol) at -15 C. After stirring for 40 min, the reaction mixture was quenched with MeOH, and concentrated. The residual oil was purified by column chromatography on silica gel (25 g, hexane-etoac 8:1) to give allylic alcohol 21 (148 mg, 80%) as a colorless oil. Methyl ether 33: To a stirred solution of alcohol 21 (785 mg, 1.09 mmol) in CH2Cl2 (4 ml) were added proton-sponge (1.61 g, 7.51 mmol) and Me3O BF4 (1.40 g, 9.47 mmol) in the dark at room temperature. The mixture was stirred at room temperature for 3 h, diluted with saturated aqueous NaHCO3 (5 ml), and extracted withetoac (3 5 ml). The combined extracts were washed with saturated aqueous citric acid (5 ml) and brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (20 g, hexane-etoac 10:1) to give methyl ether 33 (672 mg, 84%) as a colorless oil: [ ]D (c 1.02, CHCl3); IR (neat, cm -1 ) 2952, 2929, 2859, 1617, 1517, 1428, 1249, 1104, 824, 739, 701; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 13 H), 6.87 (d, J = 7.9 Hz, 2H), 5.36 (s, 1H), 5.16 (d, J = 9.7 Hz, 1H), 4.45 (d, J = 11.9 Hz, 1H), 4.41 (d, J = 11.9 Hz, 1H), 4.00 (m, 1H), 3.90 (m, 1H), 3.80 (s, 3H), (m, 2H), 3.70 (t, J = 6.7 Hz, 1H), 3.42 (m, 2H), 3.15 (s, 3H), 2.67 (m, 1H), 2.01 (m, 1H), (m, 2H), 1.69 (m, 1H), (m, 2H), 1.57 (s, 3H), (m, 2H), 1.04 (s, 9H), 0.99 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.8, 138.5, 135.8, 135.6, 133.9, 133.8, 132.6, 131.6, 129.7, 129.6, 128.4, 127.7, 127.7, 127.7, 127.6, 127.3, 113.5, 100.4, 83.4, 73.9, 73.5, 73.1, 68.6, 59.8, 55.5, 55.3, 39.6, 38.8, S14

15 37.4, 37.1, 29.1, 26.9, 21.4, 19.3, 10.5; HRMS (ESI) m/z , calcd for C46H60O6SiNa [M+Na] Alcohol 34: 4,4 -Di-tert-butylbiphenyl (209 mg, mmol) was dissolved in THF (2 ml). Lithium wire (ca. 20 mg) was cut into small pieces, washed with hexane, methanol and ether, and then added to the above solution. The reaction mixture was sonicated at 0 C for 30 min to provide deep blue color, and stirred at 0 C for 3 h. To a stirred solution of methyl ether 33 (93 mg, mmol) in THF (1 ml) was added LiDBB solution at -78 C. The mixture was stirred at -78 C for 1 h, diluted with saturated aqueous NH4Cl, and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated aqueous NaHCO3 (5 ml) and brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (14 g, hexane-etoac 5:1 to 3:1) to give alcohol 34 (65.8 mg, 81%) as a colorless oil: [ ]D (c 1.00, CHCl3); IR (neat, cm -1 ) 3458, 2951, 2930, 2859, 1616, 1519, 1428, 1250, 1171, 1112, 1062, 1036, 1011, 825, 756, 702; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 8H), 6.90 (d, J = 8.8 Hz, 2H), 5.41 (s, 1H), 5.24 (d, J = 9.2 Hz, 1H), 4.07 (m, 1H), 3.94 (m, 1H), (m, 2H), 3.82 (s, 3H), 3.75 (t, J = 7.2 Hz, 1H), (m, 2H), 3.19 (s, 3H), 2.65 (m, 1H), 2.05 (m, 1H), (m, 2H), 1.62 (m, 1H), (m, 2H), 1.60 (s, 3H), 1.48 (m, 2H), 1.09 (s, 9H), 1.03 (d, J = 6.5 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.8, 135.8, 135.6, 133.9, 133.9, 132.7, 131.6, 129.7, 129.7, 127.7, 127.7, 127.4, 113.6, 100.4, 83.4, 74.0, 73.6, 61.2, 59.9, 55.6, 55.4, 40.3, 39.6, 38.9, 37.1, 29.0, 27.0, 21.3, 19.3, 10.6; HRMS (ESI) m/z , calcd for C39H54O6SiNa [M+Na] Aldehyde 35: To a stirred solution of alcohol 34 (158 mg, mmol) were added iodobenzen diacetate (102 mg, mmol) and TEMPO (11.4 mg, mmol) at room S15

16 temperature. The mixture was stirred at room temperature for 1 h, diluted with saturated aqueous Na2S2O3, and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated aqueous NaHCO3 (5 ml) and brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (14 g, hexane-etoac 10:1 to 5:1) to give aldehyde 35 (157 mg, quant.) as a colorless oil: [ ]D (c 1.03, CHCl3); IR (neat, cm -1 ) 2948, 2931, 2851, 2720, 1726, 1616, 1517, 1428, 1342, 1249, 1104, 1035, 825, 754, 703, 616; 1 H NMR (400 MHz, CDCl3) 9.69 (dd, J = 2.2, 2.0 Hz, 1H), (m, 4H), (m, 8H), 6.88 (d, J = 8.5 Hz, 2H), 5.38 (s, 1H), 5.23 (d, J = 9.4 Hz, 1H), 4.06 (m, 1H), 3.90 (m, 1H), 3.83 (s, 3H), (m, 2H), 3.72 (t, J = 7.2 Hz, 1H), 3.16 (s, 3H), 3.07 (m, 1H), 2.42 (ddd, J = 16.2, 6.1, 2.0 Hz, 1H), 2.34 (ddd, J = 16.2, 8.1, 2.2 Hz, 1H), 1.99 (m, 1H), (m, 2H), 1.61 (s, 3H), 1.60 (m, 1H), 1.58 (dt, J = 12.1, 2.5 Hz, 1H), 1.44 (dt, J = 12.1, 11.0 Hz, 1H), 1.08 (d, J = 6.7 Hz, 3H), 1.06 (s, 9H); 13 C NMR (100 MHz, CDCl3) 201.7, 159.8, 135.7, 134.0, 134.0, 133.8, 133.6, 131.8, 129.7, 129.7, 127.8, 127.4, 113.6, 100.3, 83.3, 73.7, 73.6, 59.9, 55.7, 55.4, 51.2, 39.5, 38.9, 37.2, 27.5, 27.0, 21.3, ; HRMS (ESI) m/z , calcd for C39H52O6SiNa [M+Na] Vinyl iodide 23: To a stirred solution of CrCl2 (161 mg, 1.31 mmol) in dioxane (0.6 ml) were added a solution of aldehyde 35 (59.7 mg, 89.5 mol) and iodoform (142 mg, mmol) in dioxane (0.4 ml) at 60 C. After stirring at 60 C for 1.5 h, the mixture was diluted with cooled H2O (3 ml) and Et2O (3mL), and extracted with Et2O (3 5 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (15 g, hexane-etoac 15:1 to 8:1) to give vinyl iodide 23 (39.9 mg, 58%) as a colorless oil: [ ]D (c 1.03, CHCl3); IR (neat, cm -1 ) 2952, 2929, 2857, 1739, 1616, 1517, 1429, 1341, 1249, 1112, 1036, 950, 823, 755, 702, 615; 1 H NMR (400 MHz, CDCl3) (m, 4H), (m, 8H), 6.89 (d, J = 8.5 Hz, 2H), 6.45 (dt, J = 14.4, 6.7 Hz, 1H), 5.97 (d, J = 14.4 Hz, 1H), 5.44 (s, 1H), 5.18 (d, J = 9.4 Hz, 1H), 4.14 (m, 1H), 3.92 (m, 1H), (m, 3H), 3.81 (s, 3H), 3.16 (s, 3H), 2.58 (m, 1H), 2.10 (m, 1H), (m, 2H), (m, 2H), 1.64 (m, 1H), 1.57 (m, 1H), 1.56 (s, 3H), 1.45 (dt, J = 12.3, 11.7 Hz, S16

17 1H), 1.05 (s, 9H), 1.00 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.8, 145.2, 135.7, 134.8, 134.0, 133.1, 131.7, 129.7, 129.7, 127.8, 127.4, 113.6, 100.3, 83.4, 75.7, 73.7, 73.5, 59.9, 55.7, 55.5, 43.6, 39.6, 39.0, 37.4, 32.1, 27.1, 21.0, 19.4, 10.6; HRMS (ESI) m/z , calcd for C40H53IO5SiNa [M+Na] Alcohol 36: To a stirred solution of vinyl iodide 23 (25.9 mg, 33.7 mol) in THF (0.4 ml) was added tetrabutylammonium fluoride (TBAF) (1.0 M solution in THF, 0.06 ml, 60 mol) at room temperature. After stirring for 3 h, the mixture was diluted with saturated aqueous NH4Cl (2 ml), and extracted with EtOAc (3 3 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (4 g, hexane-etoac 2:1) to give alcohol 36 (15.3 mg, 85%) as a colorless oil: [ ]D (c 1.38, CHCl3); IR (neat, cm -1 ) 3441, 2952, 2917, 2875, 1616, 1517, 1435, 1401, 1341, 1251, 1095, 1036, 949, 828, 755, 666; 1 H NMR (400 MHz, CDCl3) 7.39 (d, J = 8.8 Hz, 2H), 6.89 (d, J = 8.8 Hz, 2H), 6.45 (dt, J = 14.6, 7.4 Hz, 1H), 5.96 (d, J = 14.6 Hz, 1H), 5.47 (s, 1H), 5.17 (d, J = 9.4 Hz, 1H), 4.15 (m, 1H), (m, 3H), 3.80 (s, 3H), 3.72 (dd, J = 8.3, 6.3 Hz, 1H), 3.15 (s, 3H), 2.57 (m, 1H), 2.08 (m, 1H), (m, 3H), 1.83 (m, 1H), (m, 3H), 1.54 (s, 3H), 0.99 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl3) 159.9, 145.2, 134.9, 133.1, 131.3, 127.3, 113.7, 100.6, 83.3, 76.2, 75.6, 73.8, 60.6, 55.6, 55.4, 43.6, 39.3, 38.1, 36.9, 32.0, 21.0, 10.6; HRMS (ESI) m/z , calcd for C24H36IO5 [M+H] Aldehyde 37: To a stirred solution of alcohol 36 (15.3 mg, 28.8 mol) in CH2Cl2 (0.3 ml) were added iodobenzen diacetate (17.2 mg, 53.4 mol) and TEMPO (1.0 mg, 6.4 mol) at room temperature. The mixture was stirred at room temperature for 5 h, S17

18 diluted with saturated aqueous Na2S2O3 (3 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated aqueous NaHCO3 (3 ml) and brine (3 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (12 g, hexane-etoac 8:1 to 4:1) to give aldehyde 37 (13.2 mg, 87%) as a colorless oil: [ ]D (c 1.40, CHCl3) IR (neat, cm -1 ) 2953, 2925, 2727, 1725, 1615, 1518, 1341, 1249, 1171, 1096, 1060, 1034, 829; 1 H NMR (400 MHz, CDCl3) 9.85 (dd, J = 2.0, 1.8 Hz, 1H), 7.40 (d, J = 8.6 Hz, 2H), 6.89 (d, J = 8.6 Hz, 2H), 6.45 (dt, J = 14.4, 7.4 Hz, 1H), 5.96 (dt, J = 14.4, 1.4 Hz, 1H), 5.50 (s, 1H), 5.17 (dq, J = 10.6, 1.1 Hz, 1H), 4.47 (m, 1H), 3.81 (m, 1H), 3.81 (s, 3H), 3.72 (dd, J = 8.5, 6.3 Hz, 1H), 3.15 (s, 3H), 2.79 (ddd, J = 16.8, 7.4, 2.0 Hz, 1H), 2.61 (ddd, J = 16.8, 5.2, 1.8 Hz, 1H), 2.56 (m, 1H), 2.09 (m, 1H), (m, 2H), 1.70 (ddd, J = 12.8, 2.5, 2.2 Hz, 1H), 1.65 (m, 1H), 1.55 (d, J =1.1 Hz, 3H), 1.52 (dt, J = 12.8, 11.0 Hz, 1H), 0.99 (d, J = 6.7 Hz, 3H); 13C NMR (100 MHz, CDCl3) 200.7, 160.0, 145.2, 135.0, 133.0, 131.0, 127.4, 113.7, 100.6, 83.3, 75.7, 73.6, 71.9, 55.7, 55.4, 49.5, 43.6, 39.3, 36.7, 32.0, 21.0, 10.6; HRMS (ESI) m/z , calcd for C24H34IO5 [M+H] Carboxylic acid 5: To a stirred solution of aldehyde 37 (45.2 mg, 85.5 mol) in t-buoh (0.8 ml) were added 2-methyl-2-butene (0.4 ml, 4.76mmol), NaClO2 (24.0 mg, mmol) and NaH2PO4 (0.1 M aqueous solution, 3.4 ml, 0.34 mmol) at room temperature. The reaction mixture was stirred at room temperature for 3 h, diluted with saturated aqueous NH4Cl (2 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with saturated brine (5 ml), dried (Na2SO4), filtered, and concentrated to give carboxylic acid 5 (42.9 mg, 92%) as a colorless oil: [ ]D (c 1.23, CHCl3); IR (neat, cm -1 ) , 2954, 2924, 1714, 1616, 1518, 1436, 1401, 1342, 1303, 1249, 1172, 1092, 1035, 948, 828, 755; 1 H NMR (400 MHz, CDCl3) 7.40 (d, J = 8.8 Hz, 2H), 6.89 (d, J =8.8 Hz, 2H), 6.44 (dt, J = 14.4, 7.2 Hz, 1H), 5.96 (dt, J = 14.4, 1.1 Hz, 1H),5.49 (s, 1H), 5.18 (d, J = 9.4 Hz, 1H), 4.37 (m, 1H), 3.80 (m, 1H), 3.80 (s, 3H), 3.74 (dd, J = 8.5, 6.3 Hz, 1H), 3.16 (s, 3H), 2.76 (dd, J = 15.9, 7.0 Hz, 1H), 2.58 (m, 1H), 2.58 (dd, J = 15.9, 5.8 Hz, 1H), 2.09 (m, 1H), (m, 2H), 1.73 (ddd, J = 13.0, Hz, 1H), 1.66 (m, 1H), 1.55 (s, 3H), 1.52 (dt, J = 13.0, 11.2 Hz, 1H), 0.99 (d, J = 6.7 Hz, S18

19 3H); 13 C NMR (100 MHz, CDCl3) 175.9, 160.0, 145.2, 135.1, 132.9, 131.0, 127.4, 113.7, 100.6, 83.3, 75.7, 73.6, 72.8, 55.6, 55.4, 43.6, 40.8, 39.3, 36.5, 32.0, 21.0, 10.6; HRMS (ESI) m/z , calcd for C24H32IO6 [M-H] Crude ester 3: To a stirred solution of carboxylic acid 5 (24.3 mg, 44.6 mol) and crude alcohol 20 (32.1 mg) in CH2Cl2 (0.6 ml) were added DMAP (2.0 mg, 16.4 mol), MNBA (25.2 mg, 73.2 mol) and NEt3 (0.04 ml, mmol) at room temperature. The mixture was stirred at room temperature for 2 h, diluted with saturated aqueous NaHCO3 (2 ml), and extracted with EtOAc (3 3 ml). The combined extracts were washed with brine (3 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (10 g, hexane-etoac 20:1 to 8:1) to give crude ester 3 (32.9 mg) as a colorless oil. Macrolactone 24: To a stirred degassed solution of crude ester 3 (23.1 mg, 23.5 mol) in DMF (6 ml) were added lithium chloride (4.2 mg, 99.1 mol) and Pd2(dba)3 (2.2 mg, 2.4 mol) at room temperature. After stirring for 2 h, the mixture was diluted with H2O (5 ml) and Et2O (2 ml), and extracted with Et2O (3 5 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on silica gel (10 g, hexane-etoac 8:1 to 6:1) to give macrolactone 24 (9.4 mg, 53% in 2 steps) as a colorless oil: [ ]D (c 0.47, CHCl3); IR (neat, cm -1 ) 2955, 2924, 1741, 1616, 1518, 1436, 1377, 1346, 1302, 1250, 1136, 1098, 1035, 990, 826, 755; 1 H NMR (400 MHz, CDCl3) 7.40 (d, J = 8.8 Hz, 2H), 6.91 (d, J = 8.8 Hz, 2H), 6.11 (dd, J = 14.8, 10.3 Hz, 1H), 5.87 (dd, J = 14.8, 12.1 Hz, 1H), 5.55 (m, 1H), (m, 4H), 5.41 (s, 1H), 5.17 (d, J = 9.8 Hz, 1H), 5.09 (d, J = 9.7 S19

20 Hz, 1H), 4.21 (m, 1H), 3.85 (m, 1H), 3.82 (s, 3H), 3.60 (m, 1H), 3.17 (s, 3H), 3.01 (dd, J = 14.6, 6.5 Hz, 1H), 2.74(dd, J = 14.6, 5.8 Hz, 1H), (m, 2H), 2.44 (m, 2H), 2.35 (m, 1H), (m, 2H), (m, 4H), 1.68 (d, J = 1.4 Hz, 3H), 1.55 (s, 3H), 1.33 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CDCl , 159.8, 139.2, 137.0, 133.8, 133.7, 132.0, 131.4, 131.1, 128.3, 127.6, 127.2, 126.6, 124.3, 113.7, 99.9, 84.3, 75.6, 74.4, 70.6, 55.8, 55.5, 42.4, 41.3, 39.8, 37.5, 36.7, 35.9, 33.1, 23.6, 22.7, 18.0, 9.8; HRMS (ESI) m/z , calcd for C35H48O6Na [M+Na] Biselyngbyolide A: To a stirred solution of macrolactone 24 (5.3 mg, 9.38 mol) in MeOH (2 ml) was added PPTS (24.0 mg, 95.5 mol) at room temperature. After stirring for 18 h, the reaction mixture was diluted with H2O (2 ml) and EtOAc (5 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by column chromatography on ODS (1 g, 100% MeOH) followed by HPLC [Nacalai Colester ( nm); flow rate 5 ml/min; detection, UV 215 nm; solvent 75% MeCN/H2O] to give biselyngbyolide A (1.7 mg, 41%, tr = 48 min) as a colorless oil: [ ]D (c 0.08, CHCl3); IR (neat, cm -1 ) , 3014, 2923, 1732, 1431, 1377, 1254, 1156, 1098, 986; 1H NMR (400 MHz, CD3OD) 5.99 (m, 2H), 5.57 (td, J = 9.0, 3.4 Hz, 1H), (m, 2H), (m, 2H), 5.18 (m, 2H), 4.08 (m, 1H), 3.75 (dd, J = 7.9, 6.5 Hz, 1H), 3.65 (m, 1H), 3.17 (s, 3H), 2.95 (dd, J = 14.4, 6.7 Hz, 1H), 2.73 (dd, J = 14.4, 6.5 Hz, 1H), 2.63 (m, 1H), (m, 5H), 1.92 (m, 1H), 1.69 (d, J = 1.7 Hz, 3H), 1.65 (m, 3H), 1.64 (m, 1H), 1.60 (m, 2H), 1.52 (d, J = 1.1 Hz, 3H), 1.43 (m, 1H), 1.03 (d, J = 6.7 Hz, 3H); 13 C NMR (100 MHz, CD3OD) 172.4, 140.3, 137.9, 133.5, 133.3, 132.1, 129.4, 128.5, 127.8, 127.4, 124.9, 87.8, 71.6, 69.4, 68.5, 55.8, 45.3, 44.4, 42.1, 41.2, 39.8, 39.7, 36.7, 34.1, 23.5, 22.4, 18.0, 10.2; HRMS (ESI) m/z , calcd for C27H42O5Na [M+Na] S20

21 (R)-MTPA ester: To a stirred solution of allylic alcohol epi-21 (2.7mg, 3.73 mol) in pyridine (0.02 ml) were added DMAP (1.0 mg, 8.19 mol) and (+)-MTPACl (0.01 ml, 52 mol) at room temperature. The mixture was stirred for 7 h, diluted with saturated aqueousaqueous NH4Cl (1 ml) and EtOAc (1 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by PLC (hexane-etoac 4:1) to give (R)-MTPA ester (2.5 mg, 71%) as a colorless oil. (S)-MTPA ester: To a stirred solution of allylic alcohol epi-21 (2.5mg, 3.46 mol) in pyridine (0.02 ml) were added DMAP (1.0 mg, 8.19 mol) and (-)-MTPACl (0.01 ml, 52 mol) at room temperature. The mixture was stirred for 8 h, diluted with saturated aqueousaqueous NH4Cl (1 ml) and EtOAc (1 ml), and extracted with EtOAc (3 5 ml). The combined extracts were washed with brine (5 ml), dried (Na2SO4), filtered, and concentrated. The residual oil was purified by PLC (hexane-etoac 4:1) to give (S)-MTPA ester (2.9 mg, 89%) as a colorless oil. S21

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