# 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 'Richard C. D. Brown' _publ_contact_author_email RCB1@SOTON.AC.UK _publ_section_title ; Synthesis of the non-adjacent bis-THF core of cis-sylvaticin using a double oxidative cyclisation ; loop_ _publ_author_name 'Richard C. D. Brown' 'Riaz Bhunnoo' 'Heather Hobbs' D.I.Laine # Attachment '04sot0866_revised1.cif' data_04sot0866 _database_code_depnum_ccdc_archive 'CCDC 697249' _chemical_compound_source 'Riaz Bhunnoo' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C28 H54 O6 Si2' _chemical_formula_weight 542.89 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' Si Si 0.0817 0.0704 '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 7.417(5) _cell_length_b 10.385(5) _cell_length_c 10.651(5) _cell_angle_alpha 68.383(5) _cell_angle_beta 83.788(5) _cell_angle_gamma 82.900(5) _cell_volume 755.1(7) _cell_formula_units_Z 1 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 3387 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description Block _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.14 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.194 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 298 _exptl_absorpt_coefficient_mu 0.155 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9786 _exptl_absorpt_correction_T_max 0.9923 _exptl_absorpt_process_details ; SADABS V2.10 (Sheldrick, G.M., 2003) ; _exptl_special_details ; SADABS was used to perform the Absorption correction Parameter refinement on 9252 reflections reduced R(int) from 0.1762 to 0.0493 Ratio of minimum to maximum apparent transmission: 0.814434 The given Tmin and Tmax were generated using the SHELX SIZE command ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker Nonius FR591 Rotating Anode' _diffrn_radiation_monochromator '10cm confocal mirrors' _diffrn_measurement_device_type 'Bruker-Nonius CCD camera on \k-goniostat' _diffrn_measurement_method '\f & \w scans to fill the asymmetric unit' _diffrn_detector_area_resol_mean 9.091 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12517 _diffrn_reflns_av_R_equivalents 0.0547 _diffrn_reflns_av_sigmaI/netI 0.0609 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.33 _diffrn_reflns_theta_max 27.63 _reflns_number_total 3491 _reflns_number_gt 2708 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'COLLECT (Hooft, R.W.W., 1998)' _computing_cell_refinement 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' _computing_data_reduction 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'CAMERON (Watkin, et al., 1993)' _computing_publication_material 'WINGX (Farrugia, 1998)' _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^)+(0.0349P)^2^+0.4161P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3491 _refine_ls_number_parameters 168 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0665 _refine_ls_R_factor_gt 0.0455 _refine_ls_wR_factor_ref 0.1072 _refine_ls_wR_factor_gt 0.0981 _refine_ls_goodness_of_fit_ref 1.018 _refine_ls_restrained_S_all 1.018 _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 Si1 Si 0.30463(6) 0.79205(5) 0.23548(5) 0.01625(14) Uani 1 1 d . . . O1 O 0.87498(18) 0.55030(15) 0.12357(15) 0.0336(3) Uani 1 1 d . . . O2 O 0.52428(15) 0.49346(12) 0.27784(12) 0.0201(3) Uani 1 1 d . . . O3 O 0.25387(15) 0.65660(11) 0.37165(12) 0.0171(3) Uani 1 1 d . . . C1 C 0.7453(3) 0.5502(2) 0.0328(2) 0.0310(5) Uani 1 1 d . . . H1A H 0.7925 0.5478 -0.0570 0.037 Uiso 1 1 calc R . . H1B H 0.6261 0.6046 0.0337 0.037 Uiso 1 1 calc R . . C2 C 0.7846(2) 0.42700(19) 0.1511(2) 0.0244(4) Uani 1 1 d . . . H2 H 0.8616 0.3494 0.1319 0.029 Uiso 1 1 calc R . . C3 C 0.6593(2) 0.38310(18) 0.27585(19) 0.0212(4) Uani 1 1 d . . . H3 H 0.7316 0.3549 0.3573 0.025 Uiso 1 1 calc R . . C4 C 0.5482(2) 0.26402(18) 0.28725(19) 0.0229(4) Uani 1 1 d . . . H4A H 0.6140 0.1725 0.3344 0.027 Uiso 1 1 calc R . . H4B H 0.5200 0.2687 0.1968 0.027 Uiso 1 1 calc R . . C5 C 0.3736(2) 0.28895(18) 0.37095(19) 0.0221(4) Uani 1 1 d . . . H5A H 0.2638 0.2957 0.3229 0.027 Uiso 1 1 calc R . . H5B H 0.3649 0.2130 0.4604 0.027 Uiso 1 1 calc R . . C6 C 0.3946(2) 0.42768(17) 0.38628(18) 0.0185(4) Uani 1 1 d . . . H6 H 0.4465 0.4087 0.4749 0.022 Uiso 1 1 calc R . . C7 C 0.2189(2) 0.52217(17) 0.37671(18) 0.0170(4) Uani 1 1 d . . . H7 H 0.1601 0.5326 0.2929 0.020 Uiso 1 1 calc R . . C8 C 0.0907(2) 0.45722(18) 0.49950(18) 0.0205(4) Uani 1 1 d . . . H8A H 0.0676 0.3642 0.5026 0.025 Uiso 1 1 calc R . . H8B H 0.1513 0.4441 0.5823 0.025 Uiso 1 1 calc R . . C9 C 0.2417(2) 0.77103(19) 0.08040(18) 0.0238(4) Uani 1 1 d . . . H9A H 0.3168 0.6921 0.0669 0.036 Uiso 1 1 calc R . . H9B H 0.2622 0.8559 0.0020 0.036 Uiso 1 1 calc R . . H9C H 0.1129 0.7541 0.0905 0.036 Uiso 1 1 calc R . . C10 C 0.5503(2) 0.81755(19) 0.22193(19) 0.0226(4) Uani 1 1 d . . . H10A H 0.5816 0.8281 0.3045 0.034 Uiso 1 1 calc R . . H10B H 0.5761 0.9013 0.1437 0.034 Uiso 1 1 calc R . . H10C H 0.6230 0.7367 0.2105 0.034 Uiso 1 1 calc R . . C11 C 0.1691(2) 0.94869(18) 0.26092(18) 0.0198(4) Uani 1 1 d . . . C12 C 0.2187(3) 1.08264(19) 0.1461(2) 0.0265(4) Uani 1 1 d . . . H12A H 0.1470 1.1625 0.1604 0.040 Uiso 1 1 calc R . . H12B H 0.1921 1.0789 0.0595 0.040 Uiso 1 1 calc R . . H12C H 0.3487 1.0923 0.1450 0.040 Uiso 1 1 calc R . . C13 C 0.2105(3) 0.9555(2) 0.3962(2) 0.0285(4) Uani 1 1 d . . . H13A H 0.3410 0.9631 0.3959 0.043 Uiso 1 1 calc R . . H13B H 0.1761 0.8710 0.4703 0.043 Uiso 1 1 calc R . . H13C H 0.1410 1.0369 0.4090 0.043 Uiso 1 1 calc R . . C14 C -0.0358(2) 0.9377(2) 0.2626(2) 0.0285(4) Uani 1 1 d . . . H14A H -0.1043 1.0191 0.2761 0.043 Uiso 1 1 calc R . . H14B H -0.0702 0.8531 0.3366 0.043 Uiso 1 1 calc R . . H14C H -0.0638 0.9340 0.1763 0.043 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 Si1 0.0163(2) 0.0150(2) 0.0165(3) -0.00434(19) -0.00019(17) -0.00283(17) O1 0.0275(7) 0.0356(8) 0.0423(9) -0.0190(7) 0.0076(6) -0.0128(6) O2 0.0174(6) 0.0164(6) 0.0246(7) -0.0066(5) 0.0052(5) -0.0020(5) O3 0.0202(6) 0.0133(6) 0.0175(6) -0.0050(5) 0.0007(5) -0.0035(4) C1 0.0281(10) 0.0323(11) 0.0294(11) -0.0091(9) 0.0059(8) -0.0035(8) C2 0.0205(9) 0.0229(10) 0.0320(11) -0.0135(8) 0.0017(8) -0.0022(7) C3 0.0204(9) 0.0197(9) 0.0240(10) -0.0096(8) -0.0033(7) 0.0028(7) C4 0.0261(9) 0.0184(9) 0.0251(10) -0.0092(8) -0.0025(7) -0.0003(7) C5 0.0253(9) 0.0170(9) 0.0244(10) -0.0081(8) -0.0001(7) -0.0028(7) C6 0.0185(8) 0.0170(9) 0.0181(9) -0.0047(7) 0.0012(7) -0.0023(6) C7 0.0183(8) 0.0134(8) 0.0196(9) -0.0056(7) 0.0007(7) -0.0048(6) C8 0.0205(9) 0.0170(9) 0.0213(9) -0.0038(7) 0.0023(7) -0.0041(7) C9 0.0272(10) 0.0224(10) 0.0208(9) -0.0056(8) -0.0033(7) -0.0038(7) C10 0.0200(9) 0.0205(9) 0.0258(10) -0.0063(8) 0.0011(7) -0.0046(7) C11 0.0207(9) 0.0147(9) 0.0218(9) -0.0042(7) 0.0000(7) -0.0023(6) C12 0.0274(10) 0.0172(9) 0.0309(11) -0.0046(8) 0.0005(8) -0.0020(7) C13 0.0360(11) 0.0230(10) 0.0278(11) -0.0119(9) -0.0006(8) -0.0003(8) C14 0.0215(9) 0.0229(10) 0.0356(12) -0.0057(9) 0.0006(8) 0.0007(7) _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 Si1 O3 1.6534(13) . ? Si1 C10 1.856(2) . ? Si1 C9 1.858(2) . ? Si1 C11 1.8952(19) . ? O1 C1 1.436(3) . ? O1 C2 1.438(2) . ? O2 C3 1.430(2) . ? O2 C6 1.437(2) . ? O3 C7 1.432(2) . ? C1 C2 1.452(3) . ? C2 C3 1.493(3) . ? C3 C4 1.531(3) . ? C4 C5 1.541(3) . ? C5 C6 1.536(2) . ? C6 C7 1.520(2) . ? C7 C8 1.519(2) . ? C8 C8 1.519(3) 2_566 ? C11 C12 1.530(3) . ? C11 C13 1.534(3) . ? C11 C14 1.536(3) . ? 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 O3 Si1 C10 110.78(7) . . ? O3 Si1 C9 110.75(8) . . ? C10 Si1 C9 110.41(9) . . ? O3 Si1 C11 105.88(8) . . ? C10 Si1 C11 108.19(8) . . ? C9 Si1 C11 110.72(8) . . ? C1 O1 C2 60.71(12) . . ? C3 O2 C6 104.30(13) . . ? C7 O3 Si1 127.25(11) . . ? O1 C1 C2 59.71(12) . . ? O1 C2 C1 59.58(13) . . ? O1 C2 C3 117.15(16) . . ? C1 C2 C3 123.45(16) . . ? O2 C3 C2 111.21(14) . . ? O2 C3 C4 103.92(14) . . ? C2 C3 C4 113.83(16) . . ? C3 C4 C5 103.12(15) . . ? C6 C5 C4 103.99(14) . . ? O2 C6 C7 110.06(14) . . ? O2 C6 C5 104.56(14) . . ? C7 C6 C5 114.30(14) . . ? O3 C7 C8 109.23(14) . . ? O3 C7 C6 110.90(13) . . ? C8 C7 C6 109.25(14) . . ? C8 C8 C7 113.90(18) 2_566 . ? C12 C11 C13 109.17(16) . . ? C12 C11 C14 108.45(14) . . ? C13 C11 C14 108.89(16) . . ? C12 C11 Si1 110.44(13) . . ? C13 C11 Si1 109.55(12) . . ? C14 C11 Si1 110.30(13) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.335 _refine_diff_density_min -0.283 _refine_diff_density_rms 0.056