Supplementary Material (ESI) for Perkin Transactions This journal is © The Royal Society of Chemistry 2002 data_PHONES _database_code_CSD 182087 _journal_coden_Cambridge 207 _publ_requested_journal 'Perkin Transactions 1' loop_ _publ_author_name 'Armstrong, Alan' 'Critchley, Trevor J.' 'Gourdel-Martin, Marie-Edith' 'Kelsey, Richard D.' 'Mortlock, Andrew A.' _publ_contact_author_name 'Dr Alan Armstrong' _publ_contact_author_address ; Department of Chemistry Imperial College South Kensington London SW7 2AY UNITED KINGDOM ; _publ_contact_author_email 'A.ARMSTRONG@IC.AC.UK' _publ_section_title ; Synthetic Studies on CP-225,917 and CP-263,114: Concise Synthesis of the Bicyclic Core using an Intramolecular Mukaiyama Aldol Reaction ; _refine_special_details ; Poor diffraction characterised by the clearly split diffraction profiles seen at 150 K was partly ameliorated by annealing and data collection at 220 K. However, the profile shape was still poor and relatively broad. This, combined with the general weakness of diffraction, meant that it was not worthwhile to collect data beyond 2theta of 45 degrees. There is disorder of the methyl group centred on C11, with the major site occupancy being 0.785(12) and the minor 0.215(12). Both C atoms were refined with isotropic displacement parameters and the O-C(methyl) distances were subject to a similarity restraint. The methyl group centred on C15 showed incipient disorder but it was decided to model this as dynamic rather than static disorder. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C17 H24 O6' _chemical_formula_sum 'C17 H24 O6' _chemical_formula_weight 324.36 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.582(7) _cell_length_b 11.418(6) _cell_length_c 11.111(7) _cell_angle_alpha 90.00 _cell_angle_beta 105.71(6) _cell_angle_gamma 90.00 _cell_volume 1658.7(16) _cell_formula_units_Z 4 _cell_measurement_temperature 220(2) _cell_measurement_reflns_used 40 _cell_measurement_theta_min 13.0 _cell_measurement_theta_max 17.5 _exptl_crystal_description Column _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.39 _exptl_crystal_size_mid 0.27 _exptl_crystal_size_min 0.27 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.299 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 0.098 _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 220(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 'Stoe Stadi-4 four-circle' _diffrn_measurement_method omega/theta _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 60 _diffrn_standards_decay_% 'random variation +/-2.4' _diffrn_reflns_number 2608 _diffrn_reflns_av_R_equivalents 0.136 _diffrn_reflns_av_sigmaI/netI 0.056 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.61 _diffrn_reflns_theta_max 22.51 _reflns_number_total 2161 _reflns_number_gt 1438 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STADI4 (Stoe & Cie, 1997a)' _computing_cell_refinement STADI4 _computing_data_reduction 'X-RED (Stoe & Cie, 1997b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1994)' _computing_publication_material 'SHELXL-97; PLATON (Spek, 2001)' _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^)+(0.021P)^2^+2.68P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary ? _atom_sites_solution_hydrogens 'placed geometrically' _refine_ls_hydrogen_treatment 'riding model' _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2161 _refine_ls_number_parameters 208 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.110 _refine_ls_R_factor_gt 0.0638 _refine_ls_wR_factor_ref 0.139 _refine_ls_wR_factor_gt 0.110 _refine_ls_goodness_of_fit_ref 1.18 _refine_ls_restrained_S_all 1.18 _refine_ls_shift/su_max 0.001 _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_symetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.4039(3) 0.5980(3) 0.1422(3) 0.0510(9) Uani 1 1 d . . . C1 C 0.3044(3) 0.4313(4) 0.1672(4) 0.0312(11) Uani 1 1 d . . . O2 O 0.2325(3) 0.4556(3) -0.2291(3) 0.0581(11) Uani 1 1 d D . . C2 C 0.2135(3) 0.4940(4) 0.1900(4) 0.0330(11) Uani 1 1 d . . . O3 O 0.2011(3) 0.6860(3) 0.2762(3) 0.0535(10) Uani 1 1 d . . . C3 C 0.1542(3) 0.5489(4) 0.0614(4) 0.0386(12) Uani 1 1 d . A . H3A H 0.0824 0.5588 0.0611 0.046 Uiso 1 1 calc R . . H3B H 0.1822 0.6271 0.0552 0.046 Uiso 1 1 calc R . . O4 O 0.1414(3) 0.4044(4) 0.3443(3) 0.0726(13) Uani 1 1 d . . . C4 C 0.1577(3) 0.4787(4) -0.0554(4) 0.0404(13) Uani 1 1 d . . . H4A H 0.0943 0.4933 -0.1210 0.048 Uiso 1 1 calc R A . H4B H 0.1596 0.3951 -0.0350 0.048 Uiso 1 1 calc R . . O5 O 0.3209(2) 0.5621(3) 0.3844(3) 0.0422(9) Uani 1 1 d . . . C5 C 0.2489(3) 0.5069(4) -0.1076(4) 0.0392(12) Uani 1 1 d D A . H5 H 0.2526 0.5930 -0.1163 0.047 Uiso 1 1 calc R . . O6 O 0.0909(2) 0.3422(3) 0.1472(3) 0.0445(9) Uani 1 1 d . . . C6 C 0.3541(4) 0.4631(4) -0.0295(4) 0.0403(12) Uani 1 1 d . . . H6 H 0.4081 0.5006 -0.0608 0.048 Uiso 1 1 calc R A . C7 C 0.3672(4) 0.3284(4) -0.0319(4) 0.0455(13) Uani 1 1 d . A . H7A H 0.3029 0.2934 -0.0808 0.055 Uiso 1 1 calc R . . H7B H 0.4201 0.3099 -0.0739 0.055 Uiso 1 1 calc R . . C8 C 0.3969(4) 0.2733(4) 0.0988(4) 0.0480(14) Uani 1 1 d . . . H8A H 0.3935 0.1877 0.0925 0.058 Uiso 1 1 calc R A . H8B H 0.4668 0.2957 0.1439 0.058 Uiso 1 1 calc R . . C9 C 0.3222(3) 0.3175(4) 0.1668(4) 0.0359(12) Uani 1 1 d . A . H9 H 0.2890 0.2653 0.2082 0.043 Uiso 1 1 calc R . . C10 C 0.3634(3) 0.5055(4) 0.1014(4) 0.0345(11) Uani 1 1 d . A . C11 C 0.1856(6) 0.5263(6) -0.3274(6) 0.058(3) Uiso 0.785(12) 1 d PD A 1 H11A H 0.1780 0.4843 -0.4052 0.086 Uiso 0.785(12) 1 calc PR A 1 H11B H 0.2269 0.5958 -0.3267 0.086 Uiso 0.785(12) 1 calc PR A 1 H11C H 0.1188 0.5491 -0.3199 0.086 Uiso 0.785(12) 1 calc PR A 1 C11' C 0.2693(19) 0.5139(18) -0.3119(16) 0.048(9) Uiso 0.215(12) 1 d PD A 2 H11D H 0.2541 0.4707 -0.3900 0.072 Uiso 0.215(12) 1 calc PR A 2 H11E H 0.3428 0.5225 -0.2794 0.072 Uiso 0.215(12) 1 calc PR A 2 H11F H 0.2379 0.5907 -0.3264 0.072 Uiso 0.215(12) 1 calc PR A 2 C12 C 0.2435(4) 0.5924(4) 0.2871(4) 0.0374(12) Uani 1 1 d . . . C13 C 0.1447(4) 0.4093(4) 0.2383(5) 0.0398(12) Uani 1 1 d . . . C14 C 0.3535(4) 0.6524(4) 0.4790(4) 0.0477(13) Uani 1 1 d . . . H14A H 0.2946 0.6809 0.5057 0.057 Uiso 1 1 calc R . . H14B H 0.3828 0.7186 0.4445 0.057 Uiso 1 1 calc R . . C15 C 0.4311(5) 0.6023(5) 0.5874(5) 0.080(2) Uani 1 1 d . . . H15A H 0.4538 0.6622 0.6508 0.119 Uiso 1 1 calc R . . H15B H 0.4890 0.5741 0.5603 0.119 Uiso 1 1 calc R . . H15C H 0.4011 0.5377 0.6221 0.119 Uiso 1 1 calc R . . C16 C 0.0280(4) 0.2511(4) 0.1802(5) 0.0480(14) Uani 1 1 d . . . H16A H -0.0287 0.2860 0.2066 0.058 Uiso 1 1 calc R . . H16B H 0.0688 0.2033 0.2490 0.058 Uiso 1 1 calc R . . C17 C -0.0121(4) 0.1773(4) 0.0660(5) 0.0548(15) Uani 1 1 d . . . H17A H -0.0548 0.1154 0.0843 0.082 Uiso 1 1 calc R . . H17B H 0.0447 0.1432 0.0410 0.082 Uiso 1 1 calc R . . H17C H -0.0523 0.2257 -0.0014 0.082 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 O1 0.054(2) 0.046(2) 0.051(2) -0.0029(19) 0.0098(18) -0.0181(19) C1 0.032(3) 0.033(3) 0.025(2) 0.001(2) 0.002(2) 0.003(2) O2 0.082(3) 0.050(2) 0.0316(19) 0.0061(18) -0.0044(19) -0.002(2) C2 0.030(3) 0.031(3) 0.038(3) -0.002(2) 0.011(2) 0.000(2) O3 0.054(2) 0.036(2) 0.066(2) -0.0084(18) 0.0090(19) 0.0135(19) C3 0.030(3) 0.037(3) 0.046(3) 0.002(2) 0.005(2) 0.000(2) O4 0.100(3) 0.078(3) 0.051(2) -0.023(2) 0.040(2) -0.044(3) C4 0.035(3) 0.042(3) 0.036(3) 0.008(2) -0.005(2) -0.005(2) O5 0.045(2) 0.037(2) 0.0406(19) -0.0124(16) 0.0041(16) 0.0019(16) C5 0.049(3) 0.035(3) 0.029(3) 0.003(2) 0.003(2) -0.008(2) O6 0.043(2) 0.046(2) 0.043(2) 0.0012(18) 0.0102(16) -0.0172(17) C6 0.038(3) 0.050(3) 0.034(3) 0.002(2) 0.010(2) -0.007(3) C7 0.045(3) 0.058(4) 0.034(3) -0.004(3) 0.011(2) 0.009(3) C8 0.058(4) 0.046(3) 0.039(3) -0.004(3) 0.012(3) 0.012(3) C9 0.040(3) 0.036(3) 0.029(3) 0.004(2) 0.006(2) 0.005(2) C10 0.025(3) 0.037(3) 0.038(3) 0.005(2) 0.002(2) 0.002(2) C12 0.036(3) 0.036(3) 0.043(3) -0.001(3) 0.014(2) -0.003(3) C13 0.042(3) 0.036(3) 0.043(3) -0.006(3) 0.015(2) 0.000(2) C14 0.052(3) 0.044(3) 0.047(3) -0.019(3) 0.013(3) -0.008(3) C15 0.081(5) 0.066(4) 0.068(4) -0.026(3) -0.020(4) 0.015(4) C16 0.044(3) 0.043(3) 0.057(3) 0.004(3) 0.014(3) -0.012(3) C17 0.047(3) 0.044(3) 0.072(4) -0.005(3) 0.013(3) -0.007(3) _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 O1 C10 1.220(5) . ? C1 C9 1.322(6) . ? C1 C10 1.487(6) . ? C1 C2 1.506(6) . ? O2 C11' 1.338(10) . ? O2 C11 1.368(7) . ? O2 C5 1.433(5) . ? C2 C12 1.535(6) . ? C2 C13 1.539(6) . ? C2 C3 1.569(6) . ? O3 C12 1.204(5) . ? C3 C4 1.537(6) . ? O4 C13 1.193(5) . ? C4 C5 1.538(6) . ? O5 C12 1.333(5) . ? O5 C14 1.454(5) . ? C5 C6 1.541(6) . ? O6 C13 1.321(5) . ? O6 C16 1.454(5) . ? C6 C10 1.505(6) . ? C6 C7 1.550(7) . ? C7 C8 1.533(6) . ? C8 C9 1.506(6) . ? C14 C15 1.484(7) . ? C16 C17 1.498(7) . ? 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 C9 C1 C10 115.8(4) . . ? C9 C1 C2 128.8(4) . . ? C10 C1 C2 112.8(4) . . ? C11' O2 C11 48.5(11) . . ? C11' O2 C5 116.9(9) . . ? C11 O2 C5 115.5(4) . . ? C1 C2 C12 113.1(4) . . ? C1 C2 C13 111.3(4) . . ? C12 C2 C13 106.6(4) . . ? C1 C2 C3 106.2(4) . . ? C12 C2 C3 108.7(4) . . ? C13 C2 C3 111.0(4) . . ? C4 C3 C2 115.8(4) . . ? C3 C4 C5 114.9(4) . . ? C12 O5 C14 114.9(4) . . ? O2 C5 C4 109.5(4) . . ? O2 C5 C6 106.4(4) . . ? C4 C5 C6 116.0(4) . . ? C13 O6 C16 117.6(4) . . ? C10 C6 C5 105.2(4) . . ? C10 C6 C7 110.8(4) . . ? C5 C6 C7 114.0(4) . . ? C8 C7 C6 113.2(4) . . ? C9 C8 C7 107.3(4) . . ? C1 C9 C8 118.7(4) . . ? O1 C10 C1 124.0(4) . . ? O1 C10 C6 123.3(4) . . ? C1 C10 C6 112.1(4) . . ? O3 C12 O5 124.2(4) . . ? O3 C12 C2 123.4(4) . . ? O5 C12 C2 112.4(4) . . ? O4 C13 O6 124.7(5) . . ? O4 C13 C2 124.2(5) . . ? O6 C13 C2 111.1(4) . . ? O5 C14 C15 108.9(4) . . ? O6 C16 C17 107.0(4) . . ? 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 C9 C1 C2 C12 130.1(5) . . . . ? C10 C1 C2 C12 -69.3(5) . . . . ? C9 C1 C2 C13 10.1(7) . . . . ? C10 C1 C2 C13 170.7(4) . . . . ? C9 C1 C2 C3 -110.8(5) . . . . ? C10 C1 C2 C3 49.8(5) . . . . ? C1 C2 C3 C4 33.0(5) . . . . ? C12 C2 C3 C4 155.0(4) . . . . ? C13 C2 C3 C4 -88.0(5) . . . . ? C2 C3 C4 C5 -88.4(5) . . . . ? C11' O2 C5 C4 146.7(14) . . . . ? C11 O2 C5 C4 92.3(6) . . . . ? C11' O2 C5 C6 -87.2(14) . . . . ? C11 O2 C5 C6 -141.7(5) . . . . ? C3 C4 C5 O2 -167.9(4) . . . . ? C3 C4 C5 C6 71.8(5) . . . . ? O2 C5 C6 C10 -173.0(4) . . . . ? C4 C5 C6 C10 -50.9(5) . . . . ? O2 C5 C6 C7 -51.3(5) . . . . ? C4 C5 C6 C7 70.7(5) . . . . ? C10 C6 C7 C8 -5.8(6) . . . . ? C5 C6 C7 C8 -124.3(4) . . . . ? C6 C7 C8 C9 50.8(6) . . . . ? C10 C1 C9 C8 -1.5(6) . . . . ? C2 C1 C9 C8 158.6(4) . . . . ? C7 C8 C9 C1 -49.4(6) . . . . ? C9 C1 C10 O1 -136.8(5) . . . . ? C2 C1 C10 O1 60.0(6) . . . . ? C9 C1 C10 C6 51.9(5) . . . . ? C2 C1 C10 C6 -111.4(4) . . . . ? C5 C6 C10 O1 -92.9(5) . . . . ? C7 C6 C10 O1 143.5(5) . . . . ? C5 C6 C10 C1 78.5(5) . . . . ? C7 C6 C10 C1 -45.1(5) . . . . ? C14 O5 C12 O3 -1.0(7) . . . . ? C14 O5 C12 C2 179.4(4) . . . . ? C1 C2 C12 O3 139.0(5) . . . . ? C13 C2 C12 O3 -98.4(5) . . . . ? C3 C2 C12 O3 21.3(6) . . . . ? C1 C2 C12 O5 -41.4(5) . . . . ? C13 C2 C12 O5 81.2(4) . . . . ? C3 C2 C12 O5 -159.1(4) . . . . ? C16 O6 C13 O4 -4.0(7) . . . . ? C16 O6 C13 C2 175.3(4) . . . . ? C1 C2 C13 O4 104.4(6) . . . . ? C12 C2 C13 O4 -19.3(7) . . . . ? C3 C2 C13 O4 -137.5(5) . . . . ? C1 C2 C13 O6 -74.9(5) . . . . ? C12 C2 C13 O6 161.3(4) . . . . ? C3 C2 C13 O6 43.1(5) . . . . ? C12 O5 C14 C15 173.5(4) . . . . ? C13 O6 C16 C17 -171.8(4) . . . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 22.51 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.22 _refine_diff_density_min -0.29 _refine_diff_density_rms 0.05