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Supporting Information for Angew. Chem. Int. Ed. Z52857 Wiley-VC 2003 69451 Weinheim, Germany

Palladium Catalyzed DYKAT of Vinyl Epoxide: Enantioselective Total Synthesis and Assignment of Configuration of (+)-Broussonetine G Barry M. Trost *, Daniel B. orne, Michael J. Woltering Department of Chemistry, Stanford University, Stanford, California, 94305-5080 Characterization Data (S)--(1-ydroxymethyl-2-propenyl)phthalimide 1 4 mp 56-57 C (PE/Et 2 ) [lit. 1 mp 58 C]; [α] D 25 = -74.2 (c=1.02, C 2 Cl 2 ); R f =0.23 (1:1 PE:Et 2 ); IR (thin film) 3464, 1774, 1710, 1468, 1388, 1360, 1064, 1027, 719 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 7.85 (m, 2), 7.74 (m, 2), 6.17 (ddd, J=17.1, 10.5, 6.6 z, 1), 5.29 (d, J=10.5 z, 1), 5.28 (d, J=17.1 z, 1), 4.94 (m, 1), 4.66 (m, 1, ), 4.15 (ddd, J=11.7, 8.7, 7.8 z, 1 ), 3.98 (ddd, J=11.7, 4.5, 3.9 z, 1) ppm; 13 C MR (75 MZ, CDCl 3 ) δ 168.5, 134.0, 131.9, 131.6, 123.3, 118.8, 62.6, 55.9 ppm. Enantiomeric excess was determined to be 98% ee by chiral PLC (Chiralpak D, 90:10 heptane:ipr, 1.0 ml/min, 13.25 min. R and 17.40 min. S). 2 (S)-2-Amino-3-buten-1-ol [α] D 25 = -19.7 (c=1.01, C 2 Cl 2 ); R f =0.25 (Me); IR (thin film) 3354, 2869, 1644, 1591, 1458, 1425, 1361, 1143, 1052, 996, 922, 859, 668 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 5.83 (ddd, J=17.4, 10.5, 5.7 z, 1), 5.24 (dd, J=17.1, 0.9 z, 1), 5.16 (dd, J=10.5, 0.9 z, 1), 3.62 (dd, J=10.2, 3.9 z, 1), 3.47 (m, 2), 3.36 (dd, J=10.2, 7.5 z, 1), 1.99 (bs, 2, 2 ) ppm; 13 C MR (75 MZ, CDCl 3 ) δ 139.3, 115.4, 66.2, 55.5 ppm. EA calculated for C 7 7 2 : C, 55.15;, 10.41;, 16.08. Found: C, 55.31;, 10.78;, 16.35. (S)-4-Vinyl-1,3-oxazolidin-2-one 5 [α] D 25 = -22.6 (c=1.07, C 2 Cl 2 ); R f =0.50 (20:1 Et 2 :Me); IR (thin film) 3286, 2988, 2914, 1748, 1647, 1538, 1480, 1401, 1349, 1320, 1290, 1236, 1095, 1050, 1024, 992, 935,

770, 724 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 6.17 (bs, 1, ), 5.83 (ddd, J=17.1, 10.2, 7.2 z, 1), 5.33 (dd, J=17.1, 0.6 z, 1), 5.26 (d, J=10.2 z, 1), 4.55 (dd, J=8.6 z, 1), 4.40 (dd, J=7.5, 0.9 z, 1), 4.07 (dd, J=8.6, 6.5 z, 1) ppm; 13 C MR (75 MZ, CDCl 3 ) δ 159.3, 135.6, 118.8, 69.9, 55.2 ppm; EA calculated for C 7 7 2 : C, 53.09;, 6.24;, 12.38. Found: C, 53.17;, 6.31;, 12.78. [4S,3(1S)]-3-(1-ydroxymethyl-propenyl)-4-vinyl-oxazolidin-2-one 6 [α] D 25 = -67.8 (c=1.14, C 2 Cl 2 ); R f =0.50 (20:1 Et 2 :Me); IR (thin film) 3418, 3085, 2985, 2912, 1732, 1644, 1480, 1417, 1336, 1253, 1064, 1030, 992, 936, 764, 706 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 5.90 (ddd, J=17.4, 10.2, 7.5 z, 1), 5.74 (ddd, J=17.7, 9.3, 8.7 z, 1), 5.38 (d, J=10.2 z, 1), 5.37 (d, J=16.8 z, 1), 5.29 (d, J=10.2 z, 1), 5.21 (d, J=17.4 z, 1), 4.48 (t, J=8.7 z, 1), 4.32 (dd, J=8.7, 8.1 z, 1), 4.02 (dd, J=8.4, 7.8 z, 1), 3.90 (m, 3), 3.57 (dd, J=8.4, 4.8 z, 1) ppm; 13 C MR (75 MZ, CDCl 3 ) δ 158.5, 134.9, 132.3, 121.7, 118.9, 67.6, 62.8, 59.6, 59.2 ppm; RMS (EI+) m/z calculated for C 9 14 3 (M + +): 184.0974, found 184.0969. Diastereomeric ratio determined by GC of crude product (Varian 3600, 100/3-10-250/2; 7.46 min. S,S and 7.69 min. S,R 92.6:7.4 anti:syn). Bn [4S,3(1S)]-3-[1-benzyloxymethyl-allyl]-4-vinyl-oxazolidin-2-one [α] D 25 = -6.2 (c=1.15, C 2 Cl 2 ); R f =0.24 (1:1 PE:Et 2 ); IR (thin film) 2959, 2928, 2885, 1752, 1463, 1335, 1110, 943, 820, 763 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 5.82 (ddd, J=17.3, 10.2, 7.5 z, 1), 5.70 (ddd, J=17.6, 8.3, 1.2 z, 1), 5.23 (m. 6), 4.60 (d, J=12.0 z, 1), 4.45 (d, J=12.0 z, 1), 4.51-4.26 (m, 3), 4.00-3.80 (m, 2), 3.62 (dd, J=10.3, 5.4 z, 1) ppm; 13 C MR (125 MZ, CDCl 3 ) δ 156.1, 135.1, 132.9m 123.5, 122.7, 122.4, 120.1, 118.3, 66.5, 65.4, 65.0, 62.1, 59.6 ppm; EA calculated for C 16 19 3 : C, 70.31;, 7.01;, 5.12. Found: C, 70.20;, 6.90;, 5.27. Bn (3S,6aS)-1,2-Dehydro-3-benzyloxymethyl-5-oxapyrrolizidin-4-one 13 m.p 156-160 C; [α] D 25 = -134.7 (c=1.01, C 2 Cl 2 ); R f =0.18 (4:1 PE:Et 2 ); IR (thin film) 2992, 2929, 1746, 1385, 1366, 1222, 1126, 1031, 746 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 7.29 (m, 5) 6.00 (d, J=6.1 z, 1), 5.93 (d, J=6.1 z, 1), 4.74 (m, 2), 4.54 (m, 3), 4.19 (dd, J=8.5, 5.1 z, 1), 3.53 (d, J=4.9 z, 2) ppm; 13 C MR (75 MZ, 2

CDCl 3 ) δ 158.2, 133.2, 127.4, 125.5, 123.6, 122.9, 122.7, 68.4, 66.4, 64.0, 62.1, 59.7 ppm; EA calculated for C 14 15 3 : C, 68.56;, 6.16;, 5.71. Found: C, 68.71;, 6.02;, 5.57. Bn (2S,5S)-(5-Benzyloxymethyl-2,5-dihydro-1-pyrrol-2-yl)-methanol [α] D 25 = -186.6 (c=0.98, C 2 Cl 2 ); R f =0.10 (20:1 C 2 Cl 2 :Me); IR (thin film) 3404, 2930, 2865, 1478, 1392, 1219, 970, 805, 740, 670 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 7.32 (m, 5), 5.78 (d, J=6.1 z, 1), 5.74 (d, J=6.1 z, 1), 4.53 (s, 2), 4.21 (bs, 2, -,-), 3.70-3.49 (m, 4), 3.45-3.34 (m, 2) ppm; 13 C MR (75 MZ, CDCl 3 ) δ 133.2, 125.9, 125.8, 123.6, 122.9, 68.4, 68.1, 61.5, 60.1, 59.7 ppm; C 13 17 2 : C, 54.19;, 5.85;, 9.03. Found: C, 53.93;, 6.03;, 8.90. RMS (EI+) m/z calculated for C 13 18 2 (M + +): 220.1338, found 220.1341. Bn Cbz (2S,5S)-2-Benzyloxymethyl-5-hydroxymethyl-2,5-dihydro-pyrrole-1-carboxylic acid benzyl ester 14 [α] D 25 = -187.2 (c=1.019, C 2 Cl 2 ); R f =0.56 (20:1 C 2 Cl 2 :Me); IR (thin film) 3428, 2920, 1701, 1454, 1416, 1356, 1318, 1105, 735, 698 cm -1 ; 1 MR (500 Mz, CDCl 3 ) 4:1 mixture of amide rotamers Major: δ 7.39-7.22 (m, 10), 5.88 (dt, J=6.3, 2.1 z, 1), 5.68 (dt, J=6.3, 1.7 z, 1), 5.08 (s, 2), 4.76 (m, 1), 4.66 (m, 1), 4.43 (d, J=12.2 z, 1), 4.38 (d, J=12.3 z, 1), 3.86 (dd, J=12.1, 1.5 z, 1), 3.68 (dd, J=9.4, 2.7 z, 1), 3.65 (dd, J=12.2, 6.3 z, 1), 3.54 (dd, J=9.3, 6.1 z, 1) ppm; Minor: δ 7.39-7.22 (m, 10), 5.98 (d, J=6.5 z, 1), 5.77 (d, J=6.5 z, 1), 5.17 (d, J=12.3 z, 1), 5.11 (d, J=12.3 z, 1), 4.76 (m, 1), 4.66 (m, 1), 4.49 (m, 2), 3.85 (m, 2) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 156.2, 138.4, 136.3, 129.8, 128.9, 128.8, 128.7, 128.6, 128.5, 128.5, 128.4, 128.0, 127.7, 73.6, 73.5, 70.6, 69.7, 69.4, 67.7, 67.3, 67.2, 66.6, 66.0, 65.4, 63.7 ppm; RMS (EI+) m/z calculated for C 21 23 4 (M + -C 2 ): 322.1446, found: 322.1443. Bn Cbz (2S,5S)-5-Benzyloxymethyl-2,5-dihydro-pyrrole-1,2-dicarboxylic acid 1-benzyl ester [α] D 25 = -204.4 (c=1.094, C 2 Cl 2 ); R f =0.10 (2:1 EtAc:PE); IR (thin film) 3400-2500, 3033, 2925, 1715, 1418, 1357, 1303, 1206, 1109, 1002, 912, 737, 698 cm -1 ; 1 MR (400 Mz, CDCl 3 ) 11:9 mixture of amide rotamers Major: δ 9.90 (bs, 1), 7.35-7.20 (m, 10), 6.04 (m, 1), 5.77 (dt, J=6.4, 2.0 z, 1), 5.12-5.04 (m, 3), 4.88 (m, 1), 4.50 (m, 2), 3.87 (dd, J=9.6, 2.9 z, 1), 3.78 (dd, J=9.6, 5.7 z, 1), 3.65 (dd, J=12.2, 6.3 z, 1), 3.54 (dd, J=9.3, 6.1 z, 1) ppm; Minor: δ 9.90 (bs, 1), 7.35-7.20 (m, 10), 6.04 (m, 1), 5.83 (dt, J=6.3, 1.8 z, 1), 5.12-5.04 (m, 3), 4.78 (m, 1), 4.70 (m, 2), 3.71 (dd, J=9.5, 2.7 z, 1), 3.55 (dd, J=9.6, 6.1 z, 1) ppm; 13 CMR (125 MZ, 3

CDCl 3 ) δ 175.4(C), 174.7(C), 154.3(C), 153.7(C), 138.1(C), 137.9(C), 136.0(C), 135.9(C), 132.5(C), 132.5(C), 128.5(C), 128.4(C), 128.3(C), 128.3(C), 128.1(C), 128.0(C), 127.9(C), 127.7(C), 127.7(C), 127.6(C), 127.5(C), 127.4(C), 124.4(C), 124.2(C), 73.3(C 2 ), 73.2(C 2 ), 70.0(C 2 ), 69.0(C 2 ), 67.6(C 2 ), 67.5(C 2 ), 67.2(C), 67.1(C), 65.3(C), 64.4(C) ppm; RMS (EI+) m/z calculated for C 21 22 5 (M + +): 368.1498, found: 368.1492. Bn Cbz Me (2S,5S)-2-Benzyloxymethyl-5-(methoxy-methyl-carbamoyl)-2,5-dihydro-pyrrole-1- carboxylic acid benzyl ester 16 [α] 25 D = -192.9 (c=7.18, CCl 3 ); R f =0.52 (2:1 EtAc:PE); IR (thin film) 3402, 2969, 2870, 1714, 1694, 1682, 1455, 1392, 1088, 1014, 915, 708 cm -1 ; 1 MR (500 Mz, CDCl 3 ) 11:9 mixture of amide rotamers Major: δ 7.35-7.23 (m, 10), 6.01 (dt, J=6.3, 2.0 z, 1), 5.73 (dt, J=6.3, 2.1 z, 1), 5.37 (m, 1), 5-18-4.96 (m, 2), 4.95 (m, 1), 4.56 (s, 2), 3.90 (dd, J=9.6, 3.1 z, 1), 3.81 (dd, J=9.5, 5.7 z, 1), 3.38 (s, 3), 3.07 (s, 3) ppm; Minor: δ 7.35-7.23 (m, 10), 5.99 (dt, J=6.3, 2.0 z, 1), 5.81 (dt, J=6.3, 2.0 z, 1), 5.51 (m, 1), 5-18-4.96 (m, 2), 4.85 (m, 1), 4.45 (d, J=12.5 z, 2), 4.41 (d, J=12.5 z, 1), 3.81 (s, 3), 3.74 (dd, J=9.5, 2.8 z, 1), 3.59 (dd, J=9.5, 6.0 z, 1), 3.23 (s, 3) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 170.0, 169.7, 154.3, 153.9, 138.2, 138.0, 136.2, 136.1, 131.7, 131.6, 128.4, 128.4, 128.3, 129.2, 128.2, 128.0, 127.9, 127.6, 127.5, 127.4, 124.5, 124.3, 73.3, 73.1, 70.3, 69.4, 67.2, 67.1, 65.7, 65.4, 65.2, 64.4, 61.3, 63.8, 32.3, 32.1 ppm; RMS (EI+) m/z calculated for C 23 27 2 5 (M + +): 411.1920, found: 411.1932. Bn Cbz (2S,5S)-2-Benzyloxymethyl-5-[5-{(5R,7R)-1,6-dioxaspiro[4.5]dec-7-yl}-pentanoyl]- 2,5-dihydro-pyrrole-1-carboxylic acid benzyl ester [α] D 26 = -206.6 (c=1.38, CCl 3 ); R f =0.22 (4:1 Et 2 :PE); IR (thin film) 2938, 2868, 1713, 1497, 1455, 1410, 1352, 1105, 1008, 737, 698 cm -1 ; 1 MR (500 Mz, CDCl 3 ) 3:2 mixture of amide rotamers Major: δ 7.37-7.22 (m, 10), 6.04 (dt, J=6.4, 2.0 z, 1), 5.65 (dt, J=6.3, 2.0 z, 1), 5.14-5.09 (m, 3), 4.89 (m, 1), 4.54 (d, J=12.2 z, 1), 4.50 (d, J=12.2 z, 1), 3.90-3.78 (m, 3), 3.73 (dd, J=9.5, 2.9 z, 1), 3.62 (m, 2), 2.25 (ddd, J=17.7, 8.7, 6.4z, 1), 2.10 (ddd, J=17.7, 8.7, 6.4 z, 1), 2.01 (m, 1), 1.92-1.75 (m, 3), 1.71-1.53 (m, 6), 1.47-1.09 (m, 6) ppm; Minor: δ 7.35-7.22 (m, 10), 6.01 (dt, J=6.4, 1.8 z, 1), 5.71 (dt, J=6.4, 1.8 z, 1), 5.00 (m, 3), 4.79 (m, 1), 4.42 (d, J=12.2 z, 1), 4.39 (d, J=12.2 z, 1), 3.90-3.78 (m, 3), 3.61 (m, 3), 2.47 (ddd, J=17.1, 10.5, 6.5 z, 1), 2.33 (ddd, J=17.1, 10.5, 6.5 z, 1), 2.01 (m, 1), 1.92-1.75 (m, 3), 1.71-1.53 (m, 6), 1.47-1.09 (m, 6) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 207.1, 206.5, 154.1, 153.6, 138.2, 138.0, 136.2, 135.9, 132.2, 132.1, 128.5, 4

128.4, 128.4, 128.3, 128.2, 128.2, 128.1, 128.1, 127.9, 127.8, 127.7, 127.6, 127.4, 126.5, 125.0, 124.9, 105.7, 74.4, 74.3, 73.3, 73.3, 73.2, 72.0, 70.2, 70.0, 69.9, 69.1, 67.3, 67.1, 66.6, 65.6, 65.4, 64.5, 38.1, 37.8, 36.9, 35.9, 32.8, 30.9, 25.2, 25.1, 23.6, 22.2, 23.1, 20.4 ppm; RMS (EI+) m/z calculated for C 33 41 6 (M + +): 277.0800, found: 277.0803; MS (ESI+) [M] + : 548.4; RMS (EI+) m/z calculated for C 20 20 3 (M + -C 13 21 3 ): 322.1443, found: 322.1445, m/z calculated for C 13 21 3 (M + -C 20 20 3 ): 225.1491, found: 225.1490. Bn Cbz (2S,5S)-2-Benzyloxymethyl-5-[(1R)-5-{(5R,7R)-1,6-dioxaspiro[4.5]dec-7-yl}-1- hydroxy-pentyl]-2,5-dihydro-pyrrole-1-carboxylic acid benzyl ester 17 [α] D 24 = -95.0 (c=1.54, CCl 3 ); R f =0.46 (1:1 EtAc:PE); IR (thin film) 3440, 3032, 2936, 1694, 1634, 1455, 1417, 1354, 1328, 1214, 1105, 1009, 958, 916, 826, 736, 698 cm -1 ; 1 MR (500 Mz, CDCl 3 ) 4:1 mixture of amide rotamers Major: δ 7.36-7.23 (m, 10), 5.88 (dt, J=6.4, 2.0 z, 1), 5.70 (dt, J=6.4, 1.8 z, 1), 5.10 (d, J=12.2 z, 1), 5.06 (d, J=12.2 z, 1), 4.87 (m, 1), 4.63 (m, 1), 4.42 (d, J=12.2, z, 1), 4.37 (d, J=12.2 z, 1), 4.12 (d, J=9.5 z, 1), 3.85 (m, 3), 3.69 (m, 2), 3.56 (dd, J=9.3, 6.0 z, 1), 2.03 (m, 1), 1.92-1.55 (m, 8), 1.44-1.11 (m, 9) ppm; Minor: δ 7.36-7.23 (m, 10), 6.02 (d, J=6.5 z, 1), 5.73 (d, J=6.5 z, 1), 5.19 (d, J=12.2 z, 1), 5.12 (d, J=12.2 z, 1), 4.74 (m, 1), 4.63 (m, 1), 4.50 (s, 2), 4.04 (m, 1), 3.85 (m, 3), 3.69 (m, 3), 2.03 (m, 1), 1.92-1.11 (m, 17) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 155.7, 138.1, 136.1, 129.5, 128.5, 128.4, 128.3, 128.2, 128.1, 128.0, 127.6, 127.5, 127.4, 105.8, 73.1, 72.6, 72.1, 70.2, 67.4, 66.6, 65.3, 37.8, 36.3, 32.9, 31.3, 30.9, 29.7, 26.4, 25.7, 23.7, 20.5 ppm; MS (ESI+) [M] + : 550.4, [M+a] + 572.4; RMS (EI+) m/z calculated for C 26 36 5 (M + -Bn): 442.2593, found: 442.2586. The absolute stereochemistry of the secondary alcohol was determined by formation of the (R)- and (S)--methylmandelates and analysis of their 1 MR spectra 2, selected data used in the analysis is shown below: δ = δr-δs Ph -0.089-0.067-0.042-0.053 Ph -0.087 Ph Me -0.120-0.208 +0.153 +0.021 5

Bn Cbz (2R,3R,4R,5R)-2-Benzyloxymethyl-5-[(1R)-5-{(5R,7R)-1,6-dioxaspiro[4.5]dec-7-yl}- 1-hydroxy-pentyl]-3,4-dihydroxy-pyrrolidine-1-carboxylic acid benzyl ester 18 [α] D 24 = -10.6 (c=0.70, CCl 3 ); R f =0.39 (2:1 EtAc:PE); IR (thin film) 3374, 2930, 1700, 1455, 1412, 1348, 1213, 1084, 1010, 736, 698 cm -1 ; 1 MR (500 Mz, CDCl 3 ) 1.3:1 mixture of amide rotamers Major: δ 7.37-7.21 (m, 10), 5.13 (m, 1), 5.06 (d, J=12.1 z, 1), 4.98 (d, J=12.2 z, 1), 4.78 (d, J=12.1 z, 1), 4.60 (m, 1), 4.44 (d, J=12.0 z, 1), 4.36 (d, J=11.8, z, 1), 4.13 (bt, J=5.7 z, 1), 4.06 (d, J=12.0 z, 1), 4.00 (m, 1), 3.87 (m, 4), 3.69 (m, 1), 3.51 (d, J=8.6 z, 1), 2.73 (bs, 1), 2.03 (m, 1), 1.85 (m, 2), 1.71-1.15 (m, 13) ppm; Minor: δ 7.36-7.21 (m, 10), 5.17 (d, J=12.4 z, 1), 5.13 (m, 1), 5.11 (d, J=12.4 z, 1), 4.84 (d, J=12.1 z, 1), 4.55 (d, J=12.0 z, 1), 4.49 (d, J=12.0 z, 1), 4.30 (dd, J=9.8, 2.8 z, 1), 4.05 (d, J=11.8 z, 1), 4.00 (m, 2), 3.87 (m, 4), 3.69 (m, 1), 3.57 (d, J=9.8 z, 1), 2.03 (m, 1), 1.85 (m, 2), 1.71-1.15 (m, 13) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 154.5, 154.3, 136.5, 136.4, 136.3, 136.2, 128.7, 128.6, 128.6, 128.6, 128.3, 128.2, 128.0, 127.9, 127.9, 105.9, 80.5, 79.6, 76.5, 75.8, 73.8, 73.6, 73.4, 72.7, 71.2, 70.1, 69.4, 69.0, 68.3, 67.6, 66.9, 66.7, 37.8, 35.9, 35.8, 34.4, 34.2, 32.8, 30.9, 29.7, 25.9, 25.7, 25.5, 25.3, 23.6, 20.4 ppm; RMS (EI+) m/z calculated for C 25 38 6 (M + -CBn): 448.2699, found: 448.2684. (+)-Broussonetine G 1 [α] D 25 = 19.3 (c=1.01, Me); R f =0.80 (5:1:1 CCl 3 :Me:56% aq. 4 ); IR (thin film 3356, 2937, 1683, 1458, 1202 cm -1 ; 1 MR (500 Mz, pyridine-d 5 ) δ 6.95 (bs, 1, -), 6.78 (bs, 1, -), 6.30 (bs, 1, -), 6.01 (bs, 1, -), 4.95 (t, J=6.4 z, 1), 4.72 (t, J=6.4 z, 1), 4.28 (dd, J=10.8, 5.5 z, 1), 4.24 (dd, J=10.8, 3.8 z, 1), 4.11 (ddd, J=6.4, 4.8, 4.8 z, 1), 3.83 (m, 4), 3.64 (dd, J=6.5, 4.8 z, 1), 2.00-1.71 (m, 6), 1.71-1.54 (m, 7), 1.48-1.37 (m, 4), 1.13 (m, 1) ppm; 13 CMR (125 MZ, pyridine-d 5 ) δ 105.9, 80.6, 80.4, 74.1, 70.3, 67.6, 66.8, 65.9, 63.5, 38.2, 36.7, 35.1, 33.4, 31.4, 26.9, 26.3, 24.1, 21.0 ppm. RMS (EI+) m/z calculated for C 18 33 6 (M + ): 359.2308, found: 359.2284. 6

1-ydroxy-dec-6-yn-5-one 3 R f =0.44 (1:1 EtAc:PE); 1 MR (300 Mz, CDCl 3 ) δ 3.65 (m, 2), 2.60 (t, J=7.2 z, 2), 2.35 (t, J=7.2 z, 2), 1.76 (m, 2), 1.68-1.55 (m, 5), 1.05 (t, J=7.2 z, 3) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 172.8, 94.4, 80.9, 62.2, 45.0, 31.8, 21.2, 20.8, 20.1, 13.4 ppm. Tr 1-Trityloxy-dec-6-yn-5-one 8 R f =0.53 (4:1 PE:Et 2 ); IR (thin film) 3059, 3032, 2961, 2872, 2212, 1674, 1491, 1449, 1223, 1161, 1073, 1034, 899, 762, 705, 648, 633 cm -1 ; 1 MR (200 Mz, CDCl 3 ) δ 7.44 (m, 6), 7.34 (m, 9), 3.07 (t, J=6.2 z, 2), 2.51 (t, J=6.5 z, 2), 2.33 (t, J=7.0 z, 2), 1.84-1.54 (m, 6), 1.00 (t, J=7.3 z, 3) ppm; 13 CMR (75 MZ, CDCl 3 ) δ 183.5, 139.6, 123.9, 122.9, 122.0, 89.4, 81.6, 76.2, 58.2, 40.5, 24.5, 16.5, 16.3, 16.1 ppm; EA calculated for C 29 30 2 : C, 84.84;, 7.37. Found: C, 84.88;, 7.30. Tr (5R)-1-Trityloxy-dec-6-yn-5-ol 9 [α] D 24 = -2.2 (c=2.63, C 2 Cl 2 ); R f =0.17 (4:1 PE:Et 2 ); IR (thin film) 3405, 3087, 2936, 2870, 1958, 1817, 1597, 1491, 1449, 1381, 1221, 1077, 1033, 900, 746, 699, 633 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 7.43 (m, 6), 7.30-7.18 (m, 9), 4.33 (bs, 1), 3.07 (t, J=6.4 z, 2), 2.16 (dt, J=2.0, 7.1 z, 2), 1.71 (d, J=3.4 z, 1, -), 1.68-1.47 (m, 8), 0.95 (t, J=7.3 z, 3) ppm; 13 CMR (75 MZ, CDCl 3 ) δ 139.7, 123.9, 122.9, 122.0, 81.6, 80.7, 76.6, 58.6, 57.9, 33.2, 24.9, 17.3, 17.2, 15.9, 8.7 ppm; RMS (EI+) m/z calculated for C 29 31 2 (M + -): 411.2324, found: 411.2321. Enantiomeric excess was determined to be 97% ee by chiral PLC (Chiralpak D, 97:3 heptane:i- Pr, 1.0 ml/min, 9.43 R and 16.97 S). Tr (5S)-1-Trityloxy-dec-9-yn-5-ol [α] 23 D = -1.4 (c=1.27, C 2 Cl 2 ); R f =0.40 (1:1 PE:Et 2 ); IR (thin film) 3584, 3388, 3058, 2937, 2867, 2116, 1959, 1821, 1597, 1490, 1449, 1266, 1074, 1032, 900, 764, 740, 707, 648, 603 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 7.43 (m, 6), 7.32-7.20 (m, 9), 3.59 (bs, 1), 3.07 (t, J=6.4 z, 2), 2.21 (dt, J=3.6, 6.3 z, 2), 1.94 (t, J=2.5 z, 1), 1.68-1.47 s(m, 11) ppm; 13 CMR (75 MZ, CDCl 3 ) δ 139.7, 123.9, 122.9, 122.1, 81.6, 79.6, 66.5, 58.6, 32.6, 31.5, 25.2, 19.8, 17.5, 13.6 ppm; RMS (EI+) m/z calculated for C 29 32 2 (M + ): 412.2402, found: 412.2416. TP Tr (5S)-1-Trityloxy-5-(Tetrahydro-pyran-2-yloxy)-dec-9-yne 7

[α] D 28 = -1.7 (c=4.80, C 2 Cl 2 ); R f =0.75 (1:1 PE:Et 2 ); IR (thin film) 3305, 3058, 2940, 2868, 1597, 1491, 1449, 1200, 1154, 1076, 1032, 1002, 902, 774, 707 cm -1 ; 1 MR (500 Mz, CDCl 3 ) Splitting complicated by mixture of TP diastereomers δ 7.44 (m, 6), 7.27 (m, 6), 7.20 (m, 3) 4.62 (m, 1), 3.87 (m, 1), 3.62 (m, 1), 3.44 (m, 1), 3.06 (m, 2), 2.19 (m, 2), 1.90 (m, 1), 1.80 (m, 1), 1.67-1.40 (m, 15) ppm; 13 CMR (75 MZ, CDCl 3 ) Double peaks due to TP diastereomers δ 144.8, 144.7, 129.0, 128.0, 127.9, 127.1, 97.9, 97.7, 86.6, 86.5, 84.9, 84.6, 76.3, 76.2, 68.8, 68.6, 63.6, 63.2, 62.9, 35.1, 34.3, 33.8, 32.7, 31.5, 31.4, 30.5, 30.4, 25.8, 24.8, 24.2, 22.9, 22.7, 22.1, 20.4, 20.2, 18.9, 18.8 ppm; RMS (EI+) m/z calculated for C 28 35 3 (M + -Ph): 419.2586, found: 419.2590; calculated for C 29 31 2 (M + -C 5 9 [TP]): 411.2324, found: 411.2308. EA calculated for C 34 40 3 : C, 82.22;, 8.12. Found: C, 81.98;, 7.97. TP Tr (5S)-1-Trityloxy-5-(tetrahydro-pyran-2-yloxy)-dodec-9-yn-12-ol [α] 26 D = -1.1 (c=1.16, C 2 Cl 2 ); R f =0.27 (1:1 PE:Et 2 ); IR (thin film) 3442, 3059, 2941, 2868, 1490, 1449, 1200, 1133, 1113, 1076, 1032, 1002, 909, 733, 707 cm -1 ; 1 MR (200 Mz, CDCl 3 ) Splitting complicated by mixture of TP diastereomers δ 7.44 (m, 6), 7.32-7.20 (m, 9), 4.63 (m, 1), 3.87 (m, 1), 3.63 (m, 3), 3.49 (m, 1), 3.06 (t, J=6.2 z, 2), 2.39 (m, 2), 2.17 (m, 2), 2.04 (bs, 1), 1.86-1.40 (m, 16) ppm; 13 CMR (50 MZ, CDCl 3 ) Double peaks due to TP diastereomers δ 142.3, 142.2, 126.4, 125.4, 124.5, 95.6, 94.8, 83.9, 79.8, 73.9, 73.5, 67.8, 61.1, 60.9, 60.5, 60.1, 59.0, 32.4, 31.7, 31.1, 30.1, 28.8, 28.7, 27.7, 23.1, 22.5, 21.9, 20.7, 20.0, 19.4, 17.6, 17.3, 16.5, 16.4 ppm; MS (+ESI) m/z calculated for C 36 44 a 4 (M + +a): 563.314, found: 563.279. EA calculated for C 36 44 4 : C, 79.96;, 8.20. Found: C, 79.86;, 7.95. (5S)-Dodec-9-yne-1,5,12-triol 10 [α] 29 D = -5.7 (c=0.42, Me); R f =0.20 (10:1 C 2 Cl 2 :Me); IR (thin film) 3333, 2937, 1457, 1434, 1374, 1335, 1048 cm -1 ; 1 MR (500 Mz, CDCl 3 ) δ 3.68 (m, 5), 2.43 (m, 2), 2.21 (m, 3), 1.73 (bs, 2), 1.67-1.43 (m, 10) ppm; 13 CMR (75 MZ, CDCl 3 ) δ 81.7, 76.8, 70.7, 62.1, 60.8, 36.5, 36.0, 32.0, 24.5, 22.7, 21.4, 18.3 ppm; EA calculated for C 12 22 3 : C, 67.26;, 10.35. Found: C, 67.16;, 10.26. 4-[(5R,7R)-1,6-Dioxaspiro[4.5]dec-7-yl]-butan-1-ol [α] 24 D = 76.2 (c=1.24, Me); R f =0.51 (10:1 C 2 Cl 2 :Me); IR (thin film) 3406, 2937, 1457, 1386, 1310, 1271, 1215, 1161, 1115, 1008, 960, 918 cm -1 ; 1 MR (500 Mz, CDCl 3 ) δ 3.88 (m, 2), 3.71 (m, 1), 3.65 (t, J=7.0 z, 2), 2.04 (m, 1), 1.94-1.81 (m, 3), 1.72-1.35 (m, 12) 1.20 (ddd, J=16.5, 13.0, 3.5 z, 1) ppm; 13 CMR (75 MZ, CDCl 3 ) δ 105.8, 70.1, 66.6, 37.7, 35.7, 32.7, 32.5, 30.8, 23.6, 21.7, 20.3 ppm; RMS 8

(EI+) m/z calculated for C 12 21 3 (M + -): 213.1491, found: 213.1491. Diastereomeric excess determined by GC of crude product (P 5973 GC/MS, 100/3-10-250/2; 7.46 min. R,R and 7.69 min. S,R 97:3). Br (5R,7S)-7-(4-Bromo-butyl)-1,6-dioxaspiro[4.5]decane 11 [α] 23 D = 64.3 (c=1.250, CCl 3 ); R f =0.81 (4:1 Et 2 :PE); IR (thin film) 2938, 2870, 1457, 1439, 1216, 1081, 1041 cm -1 ; 1 MR (300 Mz, CDCl 3 ) δ 3.88 (m, 2), 3.70 (m, 1), 3.41 (t, J=6.8z, 2), 2.04 (m, 1), 1.94-1.77 (m, 5), 1.71-1.64 (m, 4), 1.59-1.36 (m, 5), 1.21 (ddd, J=16.5, 13.0, 3.5 z, 1) ppm; 13 CMR (125 MZ, CDCl 3 ) δ 105.8, 69.8, 66.8, 37.8, 35.2, 34.0, 32.8, 32.7, 30.9, 24.3, 23.7, 20.4 ppm; RMS (EI+) m/z calculated for C 12 21 Br 2 (M + +): 277.0800, found: 277.0803. Supporting Figure 1. RTEP representation of 13. See Cambridge Crystallographic Data Centre (CCDC 21668) for the corresponding data. Refrences: [1] Trost, B.M.; Bunt, R.C.; Lemoine, R.; Calkins, T.L. J. Am. Chem. Soc. 2000, 122, 5968. [2] Trost, B.M.; Belletire, J.L.; Godleski, S.; McDougal, P.G.; Balkovec, J.M.; Baldwin, J.J.; Christy, M.E.; Ponticello, G.S.; Varga, S.L.; Springer, J.P. J. rg. Chem., 1985, 51, 2370. [3] Wedler, C.; Schick,. J. Prakt. Chem./Chem.-Ztg.. 1993, 335(5), 410. 9

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