# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Kelly Chibale' _publ_contact_author_email KELLY.CHIBALE@UCT.AC.ZA _publ_section_title ; CYCLOADDITION AND ONE-CARBON HOMOLOGATION STUDIES IN THE SYNTHESIS OF ADVANCED IRIDOID PRECURSORS ; loop_ _publ_author_name 'Kelly Chibale' 'James R. Bull' 'Anne T. Stevens' # Attachment 'B902452B_OBC_Revised_CIF_ASALC2fin' data_c:\annext1\as-alc _database_code_depnum_ccdc_archive 'CCDC 731873' _audit_creation_method SHELXL-97 _chemical_name_systematic ; (1S,2S,7R,8S,9R)-8-hydroxymethyl-10,12-dioxatricyclo- [7.2.1.027]dodec-4-ene ; _chemical_name_common ;(1S,2S,7R,8S,9R)-8-hydroxymethyl-10,12-dioxatricyclo- (7.2.1.027)dodec-4-ene ; _chemical_melting_point 80-82C _chemical_formula_moiety 'C11 H16 O3' _chemical_formula_sum 'C11 H16 O3' _chemical_formula_weight 196.24 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 0.0000 '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 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P 21 21 21' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 7.475(1) _cell_length_b 8.234(1) _cell_length_c 16.061(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 988.5(2) _cell_formula_units_Z 4 _cell_measurement_temperature 295(2) _cell_measurement_reflns_used 1291 _cell_measurement_theta_min 1.02 _cell_measurement_theta_max 27.5 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.45 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.17 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.319 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 424 _exptl_absorpt_coefficient_mu 0.095 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details none _exptl_special_details ; Since the absolute structure of the crystal selected could not be reliably determined from the dataset containing Friedel opposites, the data were merged (MERG 4 in SHELX-97). A DFIX restraint (DFIX 0.999 0.001) was applied to the O-H bond. ; _diffrn_ambient_temperature 295(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 'Nonius Kappa CCD diffractometer' _diffrn_measurement_method '1.00 deg omega and phi scans' _diffrn_reflns_number 4919 _diffrn_reflns_av_R_equivalents 0.0239 _diffrn_reflns_av_sigmaI/netI 0.0312 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.78 _diffrn_reflns_theta_max 27.48 _reflns_number_total 1326 _reflns_number_gt 1077 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT 2000' _computing_cell_refinement 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_data_reduction 'DENZO-SMN (Otwinowski & Minor, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material 'PLATON (Spek, 1990)' _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^)+(0.0346P)^2^+0.1139P] 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 none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0(10) _chemical_absolute_configuration unk _refine_ls_number_reflns 1326 _refine_ls_number_parameters 147 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0496 _refine_ls_R_factor_gt 0.0357 _refine_ls_wR_factor_ref 0.0815 _refine_ls_wR_factor_gt 0.0760 _refine_ls_goodness_of_fit_ref 1.070 _refine_ls_restrained_S_all 1.070 _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 C1 C 0.1405(2) 0.7305(2) 0.07205(13) 0.0389(5) Uani 1 1 d . . . H1 H 0.0950 0.7823 0.0214 0.047 Uiso 1 1 calc R . . C1' C 0.5276(3) 0.4739(3) 0.14123(14) 0.0396(5) Uani 1 1 d . . . H1'A H 0.529(3) 0.361(2) 0.1457(11) 0.035(5) Uiso 1 1 d . . . H1'B H 0.530(2) 0.501(2) 0.0800(13) 0.036(5) Uiso 1 1 d . . . C2 C 0.1147(3) 0.5470(2) 0.06845(13) 0.0364(4) Uani 1 1 d . . . H2 H -0.009(3) 0.531(2) 0.0666(11) 0.034(5) Uiso 1 1 d . . . O2' O 0.68498(19) 0.54167(18) 0.17813(10) 0.0521(4) Uani 1 1 d D . . H2' H 0.726(4) 0.468(3) 0.2236(13) 0.119(12) Uiso 1 1 d D . . C3 C 0.2034(3) 0.4772(3) -0.00924(12) 0.0472(5) Uani 1 1 d . . . H3A H 0.1236 0.4922 -0.0562 0.057 Uiso 1 1 calc R . . H3B H 0.3119 0.5380 -0.0205 0.057 Uiso 1 1 calc R . . C4 C 0.2496(3) 0.3005(3) -0.00248(15) 0.0521(6) Uani 1 1 d . . . H4 H 0.2885 0.2472 -0.0502 0.063 Uiso 1 1 calc R . . C5 C 0.2387(3) 0.2168(3) 0.06630(17) 0.0544(6) Uani 1 1 d . . . H5 H 0.2721 0.1081 0.0647 0.065 Uiso 1 1 calc R . . C6 C 0.1761(3) 0.2844(2) 0.14709(14) 0.0476(5) Uani 1 1 d . . . H6B H 0.2511 0.2419 0.1913 0.057 Uiso 1 1 calc R . . H6A H 0.0549 0.2474 0.1572 0.057 Uiso 1 1 calc R . . C7 C 0.1795(3) 0.4712(2) 0.15075(11) 0.0342(4) Uani 1 1 d . . . H7 H 0.0909 0.5021 0.1928 0.041 Uiso 1 1 calc R . . C8 C 0.3594(3) 0.5434(2) 0.18052(11) 0.0346(4) Uani 1 1 d . . . H8 H 0.3675 0.5237 0.2406 0.041 Uiso 1 1 calc R . . C9 C 0.3536(3) 0.7270(2) 0.16796(12) 0.0388(5) Uani 1 1 d . . . H9 H 0.465(3) 0.781(2) 0.1868(12) 0.038(5) Uiso 1 1 d . . . O10 O 0.32894(17) 0.76529(15) 0.08336(9) 0.0417(4) Uani 1 1 d . . . O11 O 0.20298(17) 0.79635(18) 0.21049(9) 0.0484(4) Uani 1 1 d . . . C12 C 0.0617(3) 0.8099(3) 0.14925(14) 0.0464(5) Uani 1 1 d . . . H12B H 0.0322 0.9228 0.1387 0.056 Uiso 1 1 calc R . . H12A H -0.0451 0.7533 0.1675 0.056 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 O10 0.0373(7) 0.0361(7) 0.0517(8) 0.0068(6) -0.0005(7) -0.0054(7) O11 0.0403(8) 0.0510(8) 0.0541(9) -0.0173(7) -0.0048(7) 0.0068(7) O2' 0.0345(8) 0.0477(8) 0.0743(11) 0.0087(8) -0.0106(8) -0.0070(8) C7 0.0313(10) 0.0322(9) 0.0391(10) 0.0035(8) 0.0050(9) -0.0027(9) C1' 0.0340(11) 0.0390(12) 0.0457(13) 0.0034(10) -0.0045(9) 0.0002(10) C2 0.0277(9) 0.0384(10) 0.0429(11) -0.0013(9) -0.0046(9) -0.0035(9) C8 0.0347(10) 0.0369(9) 0.0321(9) 0.0028(8) -0.0033(9) 0.0005(10) C3 0.0456(13) 0.0568(13) 0.0394(11) -0.0057(10) -0.0038(9) -0.0056(11) C6 0.0417(11) 0.0340(10) 0.0671(14) 0.0078(10) 0.0021(11) -0.0073(11) C1 0.0336(9) 0.0375(10) 0.0458(11) 0.0076(9) -0.0066(9) 0.0012(9) C9 0.0325(10) 0.0382(10) 0.0458(11) -0.0060(9) -0.0037(9) -0.0041(10) C12 0.0357(10) 0.0390(10) 0.0644(14) -0.0038(11) -0.0064(10) 0.0034(10) C5 0.0432(12) 0.0355(11) 0.0845(17) -0.0113(12) 0.0030(13) -0.0034(11) C4 0.0381(11) 0.0560(13) 0.0622(15) -0.0255(12) 0.0021(11) -0.0055(11) _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 O10 C9 1.407(2) . ? O10 C1 1.449(2) . ? O11 C9 1.435(2) . ? O11 C12 1.447(2) . ? O2' C1' 1.431(2) . ? O2' H2' 0.9988(11) . ? C7 C2 1.540(3) . ? C7 C6 1.540(3) . ? C7 C8 1.545(3) . ? C7 H7 0.9800 . ? C1' C8 1.519(3) . ? C1' H1'A 0.932(19) . ? C1' H1'B 1.01(2) . ? C2 C1 1.525(3) . ? C2 C3 1.525(3) . ? C2 H2 0.938(19) . ? C8 C9 1.526(3) . ? C8 H8 0.9800 . ? C3 C4 1.500(3) . ? C3 H3A 0.9700 . ? C3 H3B 0.9700 . ? C6 C5 1.487(3) . ? C6 H6B 0.9700 . ? C6 H6A 0.9700 . ? C1 C12 1.521(3) . ? C1 H1 0.9800 . ? C9 H9 0.992(19) . ? C12 H12B 0.9700 . ? C12 H12A 0.9700 . ? C5 C4 1.304(3) . ? C5 H5 0.9300 . ? C4 H4 0.9300 . ? 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 O10 C1 101.79(15) . . ? C9 O11 C12 106.24(15) . . ? C1' O2' H2' 108.5(18) . . ? C2 C7 C6 111.50(16) . . ? C2 C7 C8 112.56(15) . . ? C6 C7 C8 114.21(17) . . ? C2 C7 H7 105.9 . . ? C6 C7 H7 105.9 . . ? C8 C7 H7 105.9 . . ? O2' C1' C8 111.23(17) . . ? O2' C1' H1'A 110.4(12) . . ? C8 C1' H1'A 110.6(12) . . ? O2' C1' H1'B 107.6(11) . . ? C8 C1' H1'B 109.5(10) . . ? H1'A C1' H1'B 107.4(15) . . ? C1 C2 C3 110.44(18) . . ? C1 C2 C7 109.21(16) . . ? C3 C2 C7 114.41(16) . . ? C1 C2 H2 105.5(13) . . ? C3 C2 H2 110.5(12) . . ? C7 C2 H2 106.3(11) . . ? C1' C8 C9 109.95(17) . . ? C1' C8 C7 116.56(15) . . ? C9 C8 C7 108.38(16) . . ? C1' C8 H8 107.2 . . ? C9 C8 H8 107.2 . . ? C7 C8 H8 107.2 . . ? C4 C3 C2 113.98(19) . . ? C4 C3 H3A 108.8 . . ? C2 C3 H3A 108.8 . . ? C4 C3 H3B 108.8 . . ? C2 C3 H3B 108.8 . . ? H3A C3 H3B 107.7 . . ? C5 C6 C7 113.69(17) . . ? C5 C6 H6B 108.8 . . ? C7 C6 H6B 108.8 . . ? C5 C6 H6A 108.8 . . ? C7 C6 H6A 108.8 . . ? H6B C6 H6A 107.7 . . ? O10 C1 C12 100.92(16) . . ? O10 C1 C2 108.89(15) . . ? C12 C1 C2 114.09(18) . . ? O10 C1 H1 110.8 . . ? C12 C1 H1 110.8 . . ? C2 C1 H1 110.8 . . ? O10 C9 O11 105.52(15) . . ? O10 C9 C8 110.69(15) . . ? O11 C9 C8 110.69(17) . . ? O10 C9 H9 107.8(11) . . ? O11 C9 H9 109.6(11) . . ? C8 C9 H9 112.3(12) . . ? O11 C12 C1 103.78(15) . . ? O11 C12 H12B 111.0 . . ? C1 C12 H12B 111.0 . . ? O11 C12 H12A 111.0 . . ? C1 C12 H12A 111.0 . . ? H12B C12 H12A 109.0 . . ? C4 C5 C6 124.16(19) . . ? C4 C5 H5 117.9 . . ? C6 C5 H5 117.9 . . ? C5 C4 C3 124.0(2) . . ? C5 C4 H4 118.0 . . ? C3 C4 H4 118.0 . . ? 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 C6 C7 C2 C1 -173.71(17) . . . . ? C8 C7 C2 C1 -43.8(2) . . . . ? C6 C7 C2 C3 -49.4(2) . . . . ? C8 C7 C2 C3 80.5(2) . . . . ? O2' C1' C8 C9 60.5(2) . . . . ? O2' C1' C8 C7 -175.72(17) . . . . ? C2 C7 C8 C1' -82.0(2) . . . . ? C6 C7 C8 C1' 46.5(2) . . . . ? C2 C7 C8 C9 42.7(2) . . . . ? C6 C7 C8 C9 171.12(16) . . . . ? C1 C2 C3 C4 156.98(17) . . . . ? C7 C2 C3 C4 33.3(2) . . . . ? C2 C7 C6 C5 40.7(2) . . . . ? C8 C7 C6 C5 -88.3(2) . . . . ? C9 O10 C1 C12 45.05(17) . . . . ? C9 O10 C1 C2 -75.30(19) . . . . ? C3 C2 C1 O10 -66.1(2) . . . . ? C7 C2 C1 O10 60.5(2) . . . . ? C3 C2 C1 C12 -178.00(16) . . . . ? C7 C2 C1 C12 -51.4(2) . . . . ? C1 O10 C9 O11 -43.96(17) . . . . ? C1 O10 C9 C8 75.83(18) . . . . ? C12 O11 C9 O10 24.2(2) . . . . ? C12 O11 C9 C8 -95.62(19) . . . . ? C1' C8 C9 O10 68.0(2) . . . . ? C7 C8 C9 O10 -60.4(2) . . . . ? C1' C8 C9 O11 -175.34(15) . . . . ? C7 C8 C9 O11 56.21(19) . . . . ? C9 O11 C12 C1 4.4(2) . . . . ? O10 C1 C12 O11 -30.18(19) . . . . ? C2 C1 C12 O11 86.4(2) . . . . ? C7 C6 C5 C4 -17.8(3) . . . . ? C6 C5 C4 C3 1.0(4) . . . . ? C2 C3 C4 C5 -8.8(3) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.166 _refine_diff_density_min -0.166 _refine_diff_density_rms 0.032