Experimental procedures and spectroscopic data/physical characteristics of all compounds prepared in this work N-(Toluene-4-sulfonyl)-L-serine To a rapidly-stirred solution of L-serine (18.0 g, 171 mol, 1.0 equiv) and TsCl (43.2 g, 227 mol, 1.3 equiv) in EtOAc (400 ml) and H 2 O (120 ml) was added NaOH (228 ml of a 2 M aqueous solution, 456 mmol, 2.7 equiv) dropwise over 3 h. After a further 1 h the phases were separated and the aqueous layer acidified with c.HCl (25 ml). The resulting white

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... cipitate was filtered and dried azeotropically with toluene to yield N- (toluene-4-sulfonyl)-L-serine (26.2 g, 79%) as a colourless solid; mp 236 ºC (EtOAc); R f 0.32 (50% EtOAc-petrol); δ H (300 MHz) 7.94 (1H, d, J 8.5 Hz, NH), 7.68 (2H, d, J 8.5 Hz, ortho Ts), 7.36 (2H, d, J 8.5 Hz, meta Ts), 3.75-3.68 (1H, m, CHNHTs), 3.53-3.49 (2H, m, CH 2 OH), 2.50 (1H, s, CH 2 OH), 2.37 (3H, s, Me of Ts); m/z (CI) 277 [M+NH 4 ] + . In agreement with published data. 1 (+)-(S)-3-hydroxy-1-(4-methoxyphenyl)-2-(toluene-4-sulfonamido)propan-1-one Activated magnesium turnings (15.4 g, 632 mmol, 4.1 equiv) were suspended in THF (400 ml) and 4-bromoanisole (77.2 ml, 616 mmol, 4.0 equiv) added dropwise to maintain a steady reflux. After stirring for 1 h the mixture was transferred to a solution of acid 170 (40.0 g, 154 mmol, 1.0 equiv), and n-BuLi (193 ml of a 1.6 M solution in hexanes, 308 mmol, 2.0 equiv) in THF (400 ml) at -78 ºC. The mixture was allowed to warm to rat and after 37 h the reaction mixture was poured into HCl (1 M; 400 ml) and extracted with Teac (3 x 400 ml). The combined organic extracts were washed with saturated aqueous NaHCO 3 (600 ml) and dried (MgSO 4 ). Concentration under reduced pressure and recrystallisation (EtOAc-petrol) gave the ketone (39.0 g, 73%) as an off-white solid; mp 80-82 ºC (EtOH); R f 0.25 (10% EtOAc-CH 2 Cl 2 ); [α] D 20 +84.0 (c 1.0, EtOH); ν max (film) 3489, 3283, 3264, 1680, 1601, 1336, 1308, 1165, 910, 739 cm -1 ; δ H (300 MHz), 7.80 (2H, d, J 9.0 Hz, ortho ArOMe), 7.73 (2H, d, J 8.0 Hz, ortho Ts), 7.21 (2H, d, J 8.0 Hz, meta Ts), 6.93 (2H, d, J 9.0 Hz, meta ArOMe), 6.11 (1H, d, J 7.5 Hz, NHTs), 4.90-4.85 (1H, m, CHNHTs), 4.10-3.90 (1H, m, CHHOH), 3.88 (3H, s, ArOMe), 3.78-3.73 (1H, m, CHHOH), 2.34 (3H, s, Me of Ts); δ C (75 MHz) 202.2 (C=O), [164.5, 144.0, 136.5 (q Ar)], [131.1, 129.8, 127.1 (ArH)], 126.5 (q Ar), 114.2 (ArH), # Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 64.7 (CH 2 OH), 59.6 and 55.7 (CHNHTs and OMe of ArOMe), 21.8 (Me of Ts); m/z (CI) 367 [M+NH 4 ] + , 350 [M+H] + (Found: C, 58.49; H, 5.32; N, 3.92. C 17 H 19 NO 5 S requires C, 58.44; H, 5.48; N, 4.01%). (+)-(R)-2-(Toluene-4-sulfonamido)-3-(4-methoxyphenyl)propan-1-ol (3) (+)-(S)-3-Hydroxy-1-(4-methoxyphenyl)-2-(toluene-4-sulfonamido)propan-1-one (30.1 g, 85.9 mmol, 1.0 equiv) was dissolved in trifluoroacetic acid (132 ml, 1.72 mol, 20.0 equiv), treated dropwise with triethylsilane (137 ml, 860 mmol, 10.0 equiv) over 3 h and stirred at 40 ºC for 1 d. NaOH (2 M; 1.5 l) was then added and the mixture extracted with EtOAc (3 x 500 ml). The combined organic extracts were concentrated under reduced pressure and the resulting residue stirred with 4% NaOH−MeOH (500 ml) for 1 h. The solution was then diluted with Et 2 O (500 ml) and HCl (2 M; 500 ml) and the aqueous phase extracted with Et 2 O (2 x 500 ml). The combined organic extracts were washed with H 2 O (500 ml), brine (500 ml) and dried (MgSO 4 ). Concentration under reduced pressure and chromatography (60% Et 2 O-petrol) gave alcohol 3 (27.0 g, 93%) as a colourless oil; R f 0.65 (90% CH 2 Cl 2 -EtOAc); [α] D 20 +12.7 (c 1.3, CHCl 3 ); ν max (film) H (300 MHz) 7.59 (2H, d, J 8.0 Hz, ortho Ts), 7.22 (2H, d, J 8.0 Hz, meta Ts), 6.90 (2H, d, J 9.0 Hz, meta ArOMe), 6.72 (2H, d, J 9.0 Hz, ortho ArOMe), 4.86 (1H, d, J 7.0 Hz, NHTs), 3.79 (3H, s, OMe of ArOMe), 3.66 (1H, dd, J 15.0, 5.0 Hz, CHHOH) 3.55 (1H, dd, J 11.0, 5.0 Hz, CHHOH) 3.41-3.39 (1H, m, CHNHTs), 2.74 (1H, dd, J 14.0, 7.0 Hz, CHHArOMe), 2.62 (1H, dd, J 14.0, 8.0 Hz, CHHArOMe) 2.44 (3H, s, Me of Ts); δ C (67.5 m/z (CI) 353 [M+NH 4 ] + , 336 [M+H] + , 189 (Found: [M+H] + , 336.1272. C 17 H 21 NO 4 S requires [M+H] + , 336.1270). (+)-(R)-(E)-Ethyl 5-(4-methoxyphenyl)-4-(toluene-4-sulfonamido)pent-2-enoate To a solution of (COCl) 2 (470 µl, 5.40 mmol, 1.2 equiv) in CH 2 Cl 2 (8 ml) at -78 ºC was added DMSO (767 µl, 10.8 mmol, 2.4 equiv) in CH 2 Cl 2 (8 ml). After 5 min (+)-(R)-2-(toluene-4sulfonamido)-3-(4-methoxyphenyl)propan-1-ol (1.50 g, 4.48 mmol, 1.0 equiv) in CH 2 Cl 2 (10 ml) was added and the solution stirred at -78 ºC for 45 min. Et 3 N (3.14 ml, 22.5 mmol, 5.0 equiv) in CH 2 Cl 2 (5 ml) was then added and the solution warmed to 0 ºC over 30 min and then to rt. After 10 min the mixture was diluted with CH 2 Cl 2 (25 ml) and washed with saturated aqueous NaHCO 3 (50 ml). The aqueous layer was extracted with CH 2 Cl 2 (2 x 50 ml) and the combined organic extracts washed with H 2 O (100 ml), brine (100 ml) and dried (Na 2 SO 4 ). Concentration under reduced pressure gave the crude aldehyde as a yellow oil. This was immediately dissolved in CH 2 Cl 2 (50 ml) and to it was added Ph 3 PCHCO 2 Et (7.83 g, 22.5 mmol, 5.0 equiv). After 12 h the reaction was CHCl 3 ); ν max (film) 3502, δ H (300 MHz) 7.60 (2H, d, J 8.0 Hz, ortho Ts), 7.24 (2H, d, J 8.0 Hz, meta Ts), 6.95 (2H, d, J 8.5 Hz ortho ArOMe), 6.77 (2H, d, J 8.5 Hz, meta ArOMe), 5.64 (1H, dt, J 16.0, 4.0 Hz, CH=CHCHNHTs), 5.52 (1H, dd, J 16.0, 6.0 Hz, CH=CHCHNHTs), 4.02-4.00 (3H, m, CH 2 OH and CHNHTs), 3.81 (3H, s, OMe of ArOMe), 2.76 (2H, dd, J 14.0, 5.0 Hz, CHHArOMe), 2.66 (2H, dd, J 14.0, 7.0 Hz, CHHArOMe), 2.40 (3H, s, Me of Ts); δ C (67.5 MHz) [158.6, 143.3, 137.6 (q Ar)], 131.3, 130.6 (CH=CHCO 2 Et), [130.5, 129.5 (ArH)], 128.1 (q Ar), [127.3, 114.0 (ArH)], 62.7 (CH 2 OH), 56.4 (CHNHTs), 55.3 (OMe of ArOMe), 41.1 (CH 2 ArOMe), 21.6 (Me of Ts); m/z (CI) 379 [M+NH 4 ] + , 189, 150, 132 (Found: [M+NH 4 ] + , 379.1694. C 19 H 23 NO 4 S requires [M+NH 4 ] + , 379.1692). (+)-(3S, 4S, 5R)-5-(4-Methoxybenzyl)-1-(4-methylbenzyl)-3-(3-methylbut-2-enyl)-3-(toluene-4sulfonyl)-4-vinylpyrrolidin-2-one (10) A solution of lactams cis-1 and trans-1 (5.6:1 mixture; 332 mg, 0.680 mmol, 1.0 equiv) in DMF (5 ml) was added to KH (94.0 mg of a 35% wt dispersion in mineral oil washed with pentane, 0.820 mmol, 1.2 equiv) at 0 ºC under argon. After 15 min prenyl bromide (780 µl, 6.80 mmol, 10 equiv) was added and the mixture warmed to rt. After 20 min the reaction was quenched by dropwise addition of MeOH until the solution decolourised. Saturated aqueous NH 4 Cl (5 ml) was then added and the mixture extracted with EtOAc (5 x 10 ml). The combined organic extracts were dried (MgSO 4 ) and concentrated under reduced pressure. Chromatography (20% EtOAc−petrol) gave the lactam 10 (265 mg, 70%; 83% from cis-1) as a colourless oil; R f 0.60 (30% EtOAc−petrol); [α] D 24 +72.0 (c 0.5, CHCl 3 ); ν max (film) 1691, 1512, 1441, 1315, 1248, 1140 cm -1 ; δ H (400 MHz) 7.72 (2H,