# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Ari Koskinen' 'Kaisa Karisalmi' 'Kari Rissanen' _publ_contact_author_name 'Prof Ari Koskinen' _publ_contact_author_address ; Laboratory of Organic Chemistry Helsinki University of Technology Kemistintie 1 PO Box 6100 Espoo FIN-02015 FINLAND ; _publ_contact_author_email ARI.KOSKINEN@HUT.FI _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; An enantioselective synthesis of the C(33)-C(37) fragment of Amphotericin B ; data_7b _database_code_CSD 215705 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H24 O7 S' _chemical_formula_weight 360.41 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P21 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 5.2341(2) _cell_length_b 12.3751(5) _cell_length_c 14.2381(7) _cell_angle_alpha 90.00 _cell_angle_beta 97.6880(10) _cell_angle_gamma 90.00 _cell_volume 913.95(7) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.310 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 384 _exptl_absorpt_coefficient_mu 0.210 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5702 _diffrn_reflns_av_R_equivalents 0.0303 _diffrn_reflns_av_sigmaI/netI 0.0535 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.89 _diffrn_reflns_theta_max 25.04 _reflns_number_total 3175 _reflns_number_gt 2627 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution ? _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0500P)^2^+0.3556P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.022(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.02(11) _refine_ls_number_reflns 3175 _refine_ls_number_parameters 222 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0583 _refine_ls_R_factor_gt 0.0435 _refine_ls_wR_factor_ref 0.1099 _refine_ls_wR_factor_gt 0.1030 _refine_ls_goodness_of_fit_ref 1.021 _refine_ls_restrained_S_all 1.021 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group S1 S 0.6540(2) -0.16156(8) 0.80521(7) 0.0588(3) Uani 1 1 d . . . O14 O -0.1440(4) 0.39481(17) 0.72390(15) 0.0327(5) Uani 1 1 d . . . O8 O 0.1122(4) 0.13453(16) 0.79088(15) 0.0304(5) Uani 1 1 d . . . O13 O -0.0780(4) 0.31860(18) 0.86906(15) 0.0363(5) Uani 1 1 d . . . O11 O 0.4865(3) 0.18835(18) 0.74637(15) 0.0325(5) Uani 1 1 d . . . O20 O 0.1871(4) 0.34072(19) 0.55357(14) 0.0340(5) Uani 1 1 d . . . O19 O 0.3884(5) 0.1799(2) 0.55330(17) 0.0516(7) Uani 1 1 d . . . O4 O 0.3131(6) 0.0541(2) 0.9959(2) 0.0656(9) Uani 1 1 d . . . C9 C 0.0444(5) 0.2249(2) 0.7324(2) 0.0259(7) Uani 1 1 d . . . H9 H -0.0776 0.2035 0.6772 0.031 Uiso 1 1 calc R . . C12 C -0.0682(5) 0.3159(2) 0.7855(2) 0.0264(7) Uani 1 1 d . . . C18 C 0.3024(5) 0.2535(2) 0.5944(2) 0.0272(7) Uani 1 1 d . . . C10 C 0.3050(5) 0.2614(2) 0.7002(2) 0.0253(6) Uani 1 1 d . . . H10 H 0.3467 0.3353 0.7218 0.030 Uiso 1 1 calc R . . C7 C 0.3777(5) 0.1475(3) 0.8254(2) 0.0312(7) Uani 1 1 d . . . H7 H 0.3997 0.1997 0.8776 0.037 Uiso 1 1 calc R . . C21 C 0.1355(5) 0.3441(3) 0.4502(2) 0.0338(7) Uani 1 1 d . . . H21 H 0.2792 0.3111 0.4231 0.041 Uiso 1 1 calc R . . C3 C 0.5109(6) 0.0424(3) 0.8556(2) 0.0353(8) Uani 1 1 d . . . H3 H 0.6969 0.0564 0.8646 0.042 Uiso 1 1 calc R . . C15 C -0.2257(6) 0.4984(3) 0.7605(2) 0.0332(8) Uani 1 1 d . . . H15 H -0.3400 0.4853 0.8084 0.040 Uiso 1 1 calc R . . C4 C 0.4412(7) 0.0023(3) 0.9487(2) 0.0415(8) Uani 1 1 d . . . C16 C 0.0070(7) 0.5611(3) 0.8039(3) 0.0472(9) Uani 1 1 d . . . H16A H 0.1004 0.5195 0.8541 0.071 Uiso 1 1 calc R . . H16B H -0.0473 0.6280 0.8289 0.071 Uiso 1 1 calc R . . H16C H 0.1164 0.5757 0.7564 0.071 Uiso 1 1 calc R . . C6 C 0.5227(10) -0.1952(3) 0.9125(3) 0.0647(12) Uani 1 1 d . . . H6A H 0.3408 -0.2116 0.8969 0.078 Uiso 1 1 calc R . . H6B H 0.6082 -0.2594 0.9403 0.078 Uiso 1 1 calc R . . C23 C 0.1195(8) 0.4636(3) 0.4260(3) 0.0522(10) Uani 1 1 d . . . H23A H -0.0219 0.4956 0.4525 0.078 Uiso 1 1 calc R . . H23B H 0.0930 0.4723 0.3584 0.078 Uiso 1 1 calc R . . H23C H 0.2772 0.4985 0.4516 0.078 Uiso 1 1 calc R . . C22 C -0.1071(7) 0.2838(3) 0.4181(3) 0.0530(10) Uani 1 1 d . . . H22A H -0.0868 0.2096 0.4374 0.080 Uiso 1 1 calc R . . H22B H -0.1439 0.2874 0.3503 0.080 Uiso 1 1 calc R . . H22C H -0.2468 0.3155 0.4459 0.080 Uiso 1 1 calc R . . C2 C 0.4587(8) -0.0428(3) 0.7782(3) 0.0502(10) Uani 1 1 d . . . H2A H 0.4945 -0.0126 0.7185 0.060 Uiso 1 1 calc R . . H2B H 0.2780 -0.0629 0.7712 0.060 Uiso 1 1 calc R . . C5 C 0.5545(10) -0.1055(3) 0.9835(3) 0.0600(12) Uani 1 1 d . . . H5A H 0.7372 -0.0957 1.0043 0.072 Uiso 1 1 calc R . . H5B H 0.4750 -0.1274 1.0382 0.072 Uiso 1 1 calc R . . C17 C -0.3736(7) 0.5537(3) 0.6760(3) 0.0454(9) Uani 1 1 d . . . H17A H -0.2627 0.5644 0.6283 0.068 Uiso 1 1 calc R . . H17B H -0.4349 0.6224 0.6950 0.068 Uiso 1 1 calc R . . H17C H -0.5175 0.5096 0.6509 0.068 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 S1 0.0895(7) 0.0414(6) 0.0460(6) -0.0002(5) 0.0111(5) 0.0322(6) O14 0.0404(12) 0.0237(11) 0.0357(13) 0.0031(10) 0.0114(10) 0.0079(9) O8 0.0320(11) 0.0190(11) 0.0417(14) 0.0044(9) 0.0102(9) 0.0027(9) O13 0.0449(12) 0.0349(14) 0.0292(13) 0.0000(10) 0.0050(9) 0.0070(10) O11 0.0227(10) 0.0393(13) 0.0356(13) 0.0137(10) 0.0046(9) 0.0081(9) O20 0.0380(11) 0.0352(12) 0.0289(11) 0.0067(11) 0.0044(9) 0.0087(10) O19 0.0696(16) 0.0483(16) 0.0388(15) 0.0038(12) 0.0142(12) 0.0291(13) O4 0.113(2) 0.0460(16) 0.0452(17) 0.0066(14) 0.0364(16) 0.0272(17) C9 0.0243(14) 0.0225(16) 0.0315(17) 0.0014(13) 0.0062(12) 0.0014(11) C12 0.0235(14) 0.0219(17) 0.0337(19) 0.0012(13) 0.0039(12) -0.0005(11) C18 0.0225(14) 0.0289(17) 0.0303(17) 0.0033(14) 0.0044(12) -0.0007(13) C10 0.0224(14) 0.0206(15) 0.0323(17) 0.0031(13) 0.0020(11) -0.0001(11) C7 0.0299(15) 0.0338(18) 0.0298(17) 0.0045(14) 0.0041(12) 0.0068(13) C21 0.0298(15) 0.0424(19) 0.0287(16) 0.0048(16) 0.0024(12) 0.0023(15) C3 0.0441(18) 0.0286(18) 0.0330(19) 0.0035(15) 0.0047(14) 0.0087(14) C15 0.0345(16) 0.0239(17) 0.044(2) -0.0011(14) 0.0142(14) 0.0064(13) C4 0.057(2) 0.038(2) 0.029(2) 0.0010(16) 0.0057(16) 0.0111(17) C16 0.045(2) 0.0298(19) 0.065(3) -0.0058(18) 0.0021(17) 0.0034(15) C6 0.097(3) 0.028(2) 0.073(3) 0.015(2) 0.023(3) 0.011(2) C23 0.060(2) 0.048(2) 0.047(2) 0.0152(19) -0.0018(18) -0.0072(18) C22 0.047(2) 0.053(2) 0.055(2) 0.0132(19) -0.0090(17) -0.0099(18) C2 0.067(2) 0.044(2) 0.037(2) -0.0028(17) -0.0030(18) 0.0139(18) C5 0.095(3) 0.044(2) 0.045(2) 0.011(2) 0.021(2) 0.019(2) C17 0.048(2) 0.0286(19) 0.060(2) 0.0089(17) 0.0085(17) 0.0050(15) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag S1 C2 1.802(4) . ? S1 C6 1.805(5) . ? O14 C12 1.337(4) . ? O14 C15 1.469(4) . ? O8 C9 1.411(3) . ? O8 C7 1.419(4) . ? O13 C12 1.198(4) . ? O11 C10 1.408(3) . ? O11 C7 1.420(4) . ? O20 C18 1.331(4) . ? O20 C21 1.460(4) . ? O19 C18 1.202(4) . ? O4 C4 1.197(4) . ? C9 C12 1.519(4) . ? C9 C10 1.562(4) . ? C18 C10 1.509(4) . ? C7 C3 1.511(4) . ? C21 C22 1.491(5) . ? C21 C23 1.519(5) . ? C3 C4 1.505(5) . ? C3 C2 1.523(5) . ? C15 C17 1.504(5) . ? C15 C16 1.505(5) . ? C4 C5 1.517(5) . ? C6 C5 1.495(6) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 S1 C6 95.7(2) . . ? C12 O14 C15 118.7(2) . . ? C9 O8 C7 105.8(2) . . ? C10 O11 C7 106.3(2) . . ? C18 O20 C21 118.3(2) . . ? O8 C9 C12 112.2(2) . . ? O8 C9 C10 104.0(2) . . ? C12 C9 C10 110.1(2) . . ? O13 C12 O14 125.7(3) . . ? O13 C12 C9 125.9(3) . . ? O14 C12 C9 108.4(2) . . ? O19 C18 O20 125.4(3) . . ? O19 C18 C10 125.5(3) . . ? O20 C18 C10 109.1(2) . . ? O11 C10 C18 109.9(2) . . ? O11 C10 C9 103.8(2) . . ? C18 C10 C9 112.5(2) . . ? O8 C7 O11 104.1(2) . . ? O8 C7 C3 113.2(3) . . ? O11 C7 C3 108.3(2) . . ? O20 C21 C22 109.3(3) . . ? O20 C21 C23 104.7(3) . . ? C22 C21 C23 113.5(3) . . ? C4 C3 C7 112.2(3) . . ? C4 C3 C2 111.6(3) . . ? C7 C3 C2 111.0(3) . . ? O14 C15 C17 104.9(3) . . ? O14 C15 C16 109.7(2) . . ? C17 C15 C16 113.3(3) . . ? O4 C4 C3 122.6(3) . . ? O4 C4 C5 120.8(3) . . ? C3 C4 C5 116.5(3) . . ? C5 C6 S1 112.4(3) . . ? C3 C2 S1 111.6(2) . . ? C6 C5 C4 115.4(3) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C7 O8 C9 C12 -94.4(3) . . . . ? C7 O8 C9 C10 24.5(3) . . . . ? C15 O14 C12 O13 5.8(4) . . . . ? C15 O14 C12 C9 -171.4(2) . . . . ? O8 C9 C12 O13 7.2(4) . . . . ? C10 C9 C12 O13 -108.1(3) . . . . ? O8 C9 C12 O14 -175.6(2) . . . . ? C10 C9 C12 O14 69.1(3) . . . . ? C21 O20 C18 O19 6.6(4) . . . . ? C21 O20 C18 C10 -172.8(2) . . . . ? C7 O11 C10 C18 -143.1(2) . . . . ? C7 O11 C10 C9 -22.6(3) . . . . ? O19 C18 C10 O11 17.5(4) . . . . ? O20 C18 C10 O11 -163.1(2) . . . . ? O19 C18 C10 C9 -97.6(3) . . . . ? O20 C18 C10 C9 81.8(3) . . . . ? O8 C9 C10 O11 -1.2(3) . . . . ? C12 C9 C10 O11 119.1(3) . . . . ? O8 C9 C10 C18 117.5(2) . . . . ? C12 C9 C10 C18 -122.2(3) . . . . ? C9 O8 C7 O11 -39.5(3) . . . . ? C9 O8 C7 C3 -156.9(2) . . . . ? C10 O11 C7 O8 38.8(3) . . . . ? C10 O11 C7 C3 159.6(2) . . . . ? C18 O20 C21 C22 82.3(3) . . . . ? C18 O20 C21 C23 -155.8(3) . . . . ? O8 C7 C3 C4 -74.8(4) . . . . ? O11 C7 C3 C4 170.3(3) . . . . ? O8 C7 C3 C2 50.8(4) . . . . ? O11 C7 C3 C2 -64.1(3) . . . . ? C12 O14 C15 C17 -162.6(2) . . . . ? C12 O14 C15 C16 75.4(3) . . . . ? C7 C3 C4 O4 -6.2(5) . . . . ? C2 C3 C4 O4 -131.5(4) . . . . ? C7 C3 C4 C5 177.2(3) . . . . ? C2 C3 C4 C5 51.9(4) . . . . ? C2 S1 C6 C5 -57.8(4) . . . . ? C4 C3 C2 S1 -62.9(4) . . . . ? C7 C3 C2 S1 171.2(2) . . . . ? C6 S1 C2 C3 61.8(3) . . . . ? S1 C6 C5 C4 56.1(5) . . . . ? O4 C4 C5 C6 133.8(4) . . . . ? C3 C4 C5 C6 -49.5(5) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.04 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.533 _refine_diff_density_min -0.348 _refine_diff_density_rms 0.047