Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Christopher Moody' 'Nicola A. Boland' 'Kathy Boxall' 'Christopher J. Davis' 'Christopher S. P. McErlean' 'Nicholas Proisy' 'Swee Y. Sharp' 'A. Slawin' 'Paul Workman' _publ_contact_author_name 'Christopher Moody' _publ_contact_author_address ; School of Chemistry University of Nottingham University Park Nottingham NG7 2RD UNITED KINGDOM ; _publ_contact_author_email C.J.MOODY@NOTTINGHAM.AC.UK _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; Synthetic ansamycins prepared by a ring-expanding Claisen rearrangement. Synthesis and biological evaluation of ring and conformational analogues of the Hsp90 molecular chaperone inhibitor geldanamycin ; # Attachment 'Compound_26a.CIF' data_compound_26a _database_code_depnum_ccdc_archive 'CCDC 624769' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C24 H33 N O4' _chemical_formula_sum 'C24 H33 N O4' _chemical_formula_weight 399.51 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' N N 0.0061 0.0033 '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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.8832(12) _cell_length_b 10.3813(15) _cell_length_c 12.0879(17) _cell_angle_alpha 81.631(2) _cell_angle_beta 81.670(2) _cell_angle_gamma 78.225(2) _cell_volume 1072.0(3) _cell_formula_units_Z 2 _cell_measurement_temperature 125(2) _cell_measurement_reflns_used 225 _cell_measurement_theta_min 12 _cell_measurement_theta_max 28 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max .1 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.238 _exptl_crystal_density_method ? _exptl_crystal_F_000 432 _exptl_absorpt_coefficient_mu 0.083 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.961598 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 125(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.83 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6794 _diffrn_reflns_av_R_equivalents 0.0133 _diffrn_reflns_av_sigmaI/netI 0.0245 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.71 _diffrn_reflns_theta_max 25.45 _reflns_number_total 3816 _reflns_number_gt 3131 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0846P)^2^+1.6301P] 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 0.008(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 3816 _refine_ls_number_parameters 278 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.0834 _refine_ls_R_factor_gt 0.0681 _refine_ls_wR_factor_ref 0.1813 _refine_ls_wR_factor_gt 0.1683 _refine_ls_goodness_of_fit_ref 1.032 _refine_ls_restrained_S_all 1.032 _refine_ls_shift/su_max 0.075 _refine_ls_shift/su_mean 0.003 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 O1 O 0.4144(2) -0.25082(19) 1.13998(15) 0.0271(5) Uani 1 1 d D . . H1O H 0.5139(19) -0.261(3) 1.169(3) 0.043(10) Uiso 1 1 d D . . C1 C 0.3327(3) -0.3454(2) 1.1935(2) 0.0212(5) Uani 1 1 d . . . C2 C 0.3249(3) -0.3850(2) 1.3089(2) 0.0216(6) Uani 1 1 d . . . C3 C 0.2322(3) -0.4788(3) 1.3546(2) 0.0243(6) Uani 1 1 d . . . O3 O 0.2284(2) -0.51245(19) 1.46974(15) 0.0302(5) Uani 1 1 d . . . C4 C 0.1493(3) -0.5297(3) 1.2879(2) 0.0271(6) Uani 1 1 d . . . H4A H 0.0876 -0.5934 1.3207 0.033 Uiso 1 1 calc R . . C5 C 0.1566(3) -0.4873(3) 1.1726(2) 0.0247(6) Uani 1 1 d . . . H5A H 0.0988 -0.5210 1.1269 0.030 Uiso 1 1 calc R . . C6 C 0.2485(3) -0.3959(3) 1.1252(2) 0.0220(6) Uani 1 1 d . . . N7 N 0.2606(3) -0.3411(2) 1.01040(18) 0.0241(5) Uani 1 1 d D . . H7N H 0.317(3) -0.267(2) 0.995(3) 0.033(8) Uiso 1 1 d D . . C8 C 0.2298(3) -0.3899(3) 0.9201(2) 0.0230(6) Uani 1 1 d . . . O8 O 0.1898(2) -0.49760(19) 0.92519(16) 0.0308(5) Uani 1 1 d . . . C9 C 0.2491(3) -0.3016(3) 0.8113(2) 0.0242(6) Uani 1 1 d . . . C10 C 0.2027(3) -0.1691(3) 0.8088(2) 0.0240(6) Uani 1 1 d . . . H10A H 0.1569 -0.1372 0.8780 0.029 Uiso 1 1 calc R . . C11 C 0.2153(3) -0.0704(3) 0.7114(2) 0.0269(6) Uani 1 1 d . . . H11A H 0.2594 -0.1011 0.6414 0.032 Uiso 1 1 calc R . . C12 C 0.1697(3) 0.0607(3) 0.7125(2) 0.0290(6) Uani 1 1 d . . . H12A H 0.1860 0.1146 0.6429 0.035 Uiso 1 1 calc R . . C13 C 0.0954(3) 0.1312(3) 0.8123(2) 0.0297(6) Uani 1 1 d . . . H13A H 0.0289 0.0759 0.8625 0.036 Uiso 1 1 calc R . . H13B H 0.0289 0.2157 0.7862 0.036 Uiso 1 1 calc R . . C14 C 0.2184(5) 0.1600(4) 0.8787(3) 0.0535(11) Uani 1 1 d . . . H14A H 0.3052 0.0822 0.8713 0.064 Uiso 1 1 calc R . . O14 O 0.2840(2) 0.27037(19) 0.82061(16) 0.0295(5) Uani 1 1 d D . . H14O H 0.227(5) 0.354(3) 0.847(4) 0.092(17) Uiso 1 1 d D . . C15 C 0.1772(5) 0.1587(5) 0.9969(3) 0.0592(11) Uani 1 1 d . . . H15A H 0.1371 0.0764 1.0256 0.071 Uiso 1 1 calc R . . H15B H 0.0907 0.2340 1.0097 0.071 Uiso 1 1 calc R . . C16 C 0.3020(4) 0.1669(3) 1.0674(3) 0.0395(8) Uani 1 1 d . . . H16A H 0.4012 0.1133 1.0378 0.047 Uiso 1 1 calc R . . H16B H 0.3160 0.2600 1.0607 0.047 Uiso 1 1 calc R . . C17 C 0.2631(4) 0.1180(4) 1.1898(3) 0.0429(8) Uani 1 1 d . . . H17A H 0.1585 0.1651 1.2166 0.052 Uiso 1 1 calc R . . H17B H 0.2596 0.0225 1.1968 0.052 Uiso 1 1 calc R . . C18 C 0.3758(3) 0.1374(3) 1.2646(2) 0.0289(6) Uani 1 1 d . . . H18A H 0.3614 0.2330 1.2722 0.035 Uiso 1 1 calc R . . H18B H 0.4825 0.1093 1.2283 0.035 Uiso 1 1 calc R . . C19 C 0.3579(4) 0.0596(3) 1.3832(2) 0.0303(6) Uani 1 1 d . . . H19A H 0.4192 0.0904 1.4328 0.036 Uiso 1 1 calc R . . H19B H 0.2478 0.0769 1.4157 0.036 Uiso 1 1 calc R . . C20 C 0.4119(3) -0.0868(3) 1.3781(2) 0.0249(6) Uani 1 1 d . . . H20A H 0.5194 -0.1140 1.3559 0.030 Uiso 1 1 calc R . . C21 C 0.3302(3) -0.1833(3) 1.4005(2) 0.0229(6) Uani 1 1 d . . . C22 C 0.4087(3) -0.3246(3) 1.3831(2) 0.0224(6) Uani 1 1 d . . . H22A H 0.5167 -0.3250 1.3481 0.027 Uiso 1 1 calc R . . H22B H 0.4121 -0.3795 1.4572 0.027 Uiso 1 1 calc R . . C23 C 0.1730(4) -0.6298(3) 1.5176(2) 0.0337(7) Uani 1 1 d . . . H23A H 0.0642 -0.6202 1.5058 0.051 Uiso 1 1 calc R . . H23B H 0.1819 -0.6448 1.5986 0.051 Uiso 1 1 calc R . . H23C H 0.2347 -0.7054 1.4816 0.051 Uiso 1 1 calc R . . C24 C 0.3140(4) -0.3732(3) 0.7104(2) 0.0383(8) Uani 1 1 d . . . H24A H 0.2414 -0.4272 0.6971 0.057 Uiso 1 1 calc R . . H24B H 0.4133 -0.4306 0.7242 0.057 Uiso 1 1 calc R . . H24C H 0.3296 -0.3085 0.6442 0.057 Uiso 1 1 calc R . . C25 C 0.1592(3) -0.1644(3) 1.4398(3) 0.0334(7) Uani 1 1 d . . . H25A H 0.1212 -0.0730 1.4566 0.050 Uiso 1 1 calc R . . H25B H 0.1408 -0.2257 1.5079 0.050 Uiso 1 1 calc R . . H25C H 0.1043 -0.1820 1.3805 0.050 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 0.0329(11) 0.0306(10) 0.0203(9) 0.0017(8) -0.0029(8) -0.0157(8) C1 0.0206(13) 0.0204(12) 0.0213(13) -0.0025(10) 0.0008(10) -0.0034(10) C2 0.0223(13) 0.0216(13) 0.0205(13) -0.0025(10) -0.0022(10) -0.0031(10) C3 0.0283(14) 0.0224(13) 0.0208(13) -0.0017(10) 0.0014(11) -0.0050(11) O3 0.0435(12) 0.0291(10) 0.0194(9) 0.0011(8) -0.0005(8) -0.0151(9) C4 0.0321(15) 0.0233(13) 0.0265(14) -0.0023(11) 0.0010(11) -0.0101(11) C5 0.0278(14) 0.0224(13) 0.0254(14) -0.0050(10) -0.0037(11) -0.0065(11) C6 0.0231(13) 0.0224(13) 0.0195(12) -0.0039(10) -0.0017(10) -0.0018(10) N7 0.0310(13) 0.0228(11) 0.0199(11) -0.0015(9) -0.0040(9) -0.0087(9) C8 0.0236(13) 0.0231(13) 0.0229(13) -0.0054(10) -0.0039(10) -0.0029(11) O8 0.0428(12) 0.0247(10) 0.0274(10) -0.0063(8) -0.0046(9) -0.0097(9) C9 0.0269(14) 0.0256(14) 0.0206(13) -0.0038(10) -0.0046(10) -0.0042(11) C10 0.0241(14) 0.0267(14) 0.0224(13) -0.0044(10) -0.0049(10) -0.0051(11) C11 0.0272(14) 0.0281(14) 0.0243(14) -0.0031(11) -0.0029(11) -0.0030(11) C12 0.0269(14) 0.0305(15) 0.0291(15) 0.0034(11) -0.0056(11) -0.0073(12) C13 0.0357(16) 0.0241(14) 0.0311(15) -0.0033(11) -0.0043(12) -0.0095(12) C14 0.083(3) 0.057(2) 0.0350(18) 0.0172(16) -0.0231(18) -0.051(2) O14 0.0412(12) 0.0269(10) 0.0232(10) -0.0011(8) -0.0005(8) -0.0164(9) C15 0.065(3) 0.075(3) 0.045(2) 0.0169(19) -0.0179(18) -0.036(2) C16 0.052(2) 0.0409(18) 0.0302(16) 0.0058(13) -0.0092(14) -0.0235(15) C17 0.0402(18) 0.056(2) 0.0356(17) 0.0164(15) -0.0145(14) -0.0251(16) C18 0.0335(16) 0.0251(14) 0.0272(14) 0.0002(11) -0.0031(12) -0.0055(12) C19 0.0404(17) 0.0256(14) 0.0251(14) -0.0032(11) -0.0044(12) -0.0059(12) C20 0.0288(14) 0.0280(14) 0.0173(12) -0.0020(10) -0.0043(10) -0.0032(11) C21 0.0243(13) 0.0297(14) 0.0144(12) -0.0024(10) -0.0044(10) -0.0031(11) C22 0.0242(13) 0.0235(13) 0.0194(12) -0.0028(10) -0.0025(10) -0.0044(10) C23 0.0477(18) 0.0228(14) 0.0284(15) 0.0028(11) 0.0014(13) -0.0098(13) C24 0.057(2) 0.0306(15) 0.0212(14) -0.0065(12) -0.0018(13) 0.0057(14) C25 0.0282(15) 0.0378(16) 0.0361(16) -0.0102(13) -0.0043(12) -0.0060(13) _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 C1 1.371(3) . ? C1 C2 1.391(4) . ? C1 C6 1.407(4) . ? C2 C3 1.404(4) . ? C2 C22 1.517(4) . ? C3 O3 1.382(3) . ? C3 C4 1.388(4) . ? O3 C23 1.421(3) . ? C4 C5 1.395(4) . ? C5 C6 1.385(4) . ? C6 N7 1.419(3) . ? N7 C8 1.352(3) . ? C8 O8 1.231(3) . ? C8 C9 1.499(4) . ? C9 C10 1.350(4) . ? C9 C24 1.503(4) . ? C10 C11 1.451(4) . ? C11 C12 1.339(4) . ? C12 C13 1.502(4) . ? C13 C14 1.545(4) . ? C14 C15 1.421(5) . ? C14 O14 1.437(4) . ? C15 C16 1.515(5) . ? C16 C17 1.508(4) . ? C17 C18 1.503(4) . ? C18 C19 1.543(4) . ? C19 C20 1.505(4) . ? C20 C21 1.329(4) . ? C21 C25 1.506(4) . ? C21 C22 1.520(4) . ? 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 O1 C1 C2 123.1(2) . . ? O1 C1 C6 115.7(2) . . ? C2 C1 C6 121.2(2) . . ? C1 C2 C3 117.7(2) . . ? C1 C2 C22 121.0(2) . . ? C3 C2 C22 121.3(2) . . ? O3 C3 C4 123.8(2) . . ? O3 C3 C2 114.6(2) . . ? C4 C3 C2 121.6(2) . . ? C3 O3 C23 117.7(2) . . ? C3 C4 C5 119.9(2) . . ? C6 C5 C4 119.6(2) . . ? C5 C6 C1 119.9(2) . . ? C5 C6 N7 125.0(2) . . ? C1 C6 N7 115.0(2) . . ? C8 N7 C6 128.9(2) . . ? O8 C8 N7 123.7(2) . . ? O8 C8 C9 122.1(2) . . ? N7 C8 C9 114.2(2) . . ? C10 C9 C8 120.0(2) . . ? C10 C9 C24 125.2(2) . . ? C8 C9 C24 114.7(2) . . ? C9 C10 C11 126.9(3) . . ? C12 C11 C10 125.1(3) . . ? C11 C12 C13 126.8(3) . . ? C12 C13 C14 111.3(3) . . ? C15 C14 O14 116.8(3) . . ? C15 C14 C13 116.0(3) . . ? O14 C14 C13 110.2(2) . . ? C14 C15 C16 117.7(3) . . ? C17 C16 C15 112.3(3) . . ? C18 C17 C16 113.9(3) . . ? C17 C18 C19 113.5(2) . . ? C20 C19 C18 110.8(2) . . ? C21 C20 C19 129.1(3) . . ? C20 C21 C25 124.9(3) . . ? C20 C21 C22 119.8(2) . . ? C25 C21 C22 115.3(2) . . ? C2 C22 C21 112.1(2) . . ? 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 O1 C1 C2 C3 177.4(2) . . . . ? C6 C1 C2 C3 1.1(4) . . . . ? O1 C1 C2 C22 -0.2(4) . . . . ? C6 C1 C2 C22 -176.5(2) . . . . ? C1 C2 C3 O3 -179.3(2) . . . . ? C22 C2 C3 O3 -1.7(4) . . . . ? C1 C2 C3 C4 -0.8(4) . . . . ? C22 C2 C3 C4 176.8(2) . . . . ? C4 C3 O3 C23 18.0(4) . . . . ? C2 C3 O3 C23 -163.5(2) . . . . ? O3 C3 C4 C5 178.2(2) . . . . ? C2 C3 C4 C5 -0.2(4) . . . . ? C3 C4 C5 C6 0.9(4) . . . . ? C4 C5 C6 C1 -0.6(4) . . . . ? C4 C5 C6 N7 -177.2(2) . . . . ? O1 C1 C6 C5 -177.0(2) . . . . ? C2 C1 C6 C5 -0.4(4) . . . . ? O1 C1 C6 N7 0.0(3) . . . . ? C2 C1 C6 N7 176.5(2) . . . . ? C5 C6 N7 C8 -22.2(4) . . . . ? C1 C6 N7 C8 161.0(3) . . . . ? C6 N7 C8 O8 -2.9(4) . . . . ? C6 N7 C8 C9 177.4(2) . . . . ? O8 C8 C9 C10 140.6(3) . . . . ? N7 C8 C9 C10 -39.7(4) . . . . ? O8 C8 C9 C24 -36.4(4) . . . . ? N7 C8 C9 C24 143.2(3) . . . . ? C8 C9 C10 C11 179.0(3) . . . . ? C24 C9 C10 C11 -4.3(5) . . . . ? C9 C10 C11 C12 -179.1(3) . . . . ? C10 C11 C12 C13 -0.9(5) . . . . ? C11 C12 C13 C14 87.0(4) . . . . ? C12 C13 C14 C15 -147.8(4) . . . . ? C12 C13 C14 O14 76.7(4) . . . . ? O14 C14 C15 C16 -56.0(6) . . . . ? C13 C14 C15 C16 171.5(3) . . . . ? C14 C15 C16 C17 -160.1(4) . . . . ? C15 C16 C17 C18 -174.1(3) . . . . ? C16 C17 C18 C19 -166.7(3) . . . . ? C17 C18 C19 C20 70.7(3) . . . . ? C18 C19 C20 C21 -114.1(3) . . . . ? C19 C20 C21 C25 -1.5(4) . . . . ? C19 C20 C21 C22 176.5(2) . . . . ? C1 C2 C22 C21 73.0(3) . . . . ? C3 C2 C22 C21 -104.5(3) . . . . ? C20 C21 C22 C2 -126.6(3) . . . . ? C25 C21 C22 C2 51.6(3) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O1 H1O O14 0.9800(11) 1.799(11) 2.751(3) 163(3) 2_657 N7 H7N O1 0.9799(11) 2.10(3) 2.602(3) 110(2) . O14 H14O O8 0.9799(10) 1.87(2) 2.803(3) 158(4) 1_565 _diffrn_measured_fraction_theta_max 0.961 _diffrn_reflns_theta_full 25.45 _diffrn_measured_fraction_theta_full 0.961 _refine_diff_density_max 1.515 _refine_diff_density_min -0.603 _refine_diff_density_rms 0.063