# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2010 data_global _journal_name_full Synlett _journal_coden_Cambridge 1088 _journal_year 2007 _journal_page_first 2371 _publ_contact_author_name 'Hans-Joachim Knolker' _publ_contact_author_address ; Institut fur Organische Chemie Technische Universitat Dresden Bergstrasse 66 Dresden 01069 GERMANY ; _publ_contact_author_email HANS-JOACHIM.KNOELKER@CHEMIE.TU-DRESDEN.DE _publ_section_title ; Stereoselective total synthesis of the sesquiterpene (+/-)-beta-isocomene ; loop_ _publ_author_name 'Arndt W. Schmidt' 'Thomas Olpp' 'Elke Baum' 'Tina Stiffel' 'Hans-Joachim Knolker' data_olpp1 _database_code_depnum_ccdc_archive 'CCDC 646230' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29 H38 O Si' _chemical_formula_weight 430.68 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' Si Si 0.0817 0.0704 '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 'P 21/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 13.4071(14) _cell_length_b 12.1653(9) _cell_length_c 16.2492(17) _cell_angle_alpha 90.00 _cell_angle_beta 109.414(11) _cell_angle_gamma 90.00 _cell_volume 2499.6(4) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 8000 _cell_measurement_theta_min 2 _cell_measurement_theta_max 26 _exptl_crystal_description fragment _exptl_crystal_colour colourless _exptl_crystal_size_max 0.60 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.144 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 936 _exptl_absorpt_coefficient_mu 0.112 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.9359 _exptl_absorpt_correction_T_max 0.9566 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(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 IPDS' _diffrn_measurement_method 'area detector' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 18979 _diffrn_reflns_av_R_equivalents 0.0393 _diffrn_reflns_av_sigmaI/netI 0.0278 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.14 _diffrn_reflns_theta_max 25.85 _reflns_number_total 4787 _reflns_number_gt 4004 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE Software' _computing_cell_refinement 'STOE Software' _computing_data_reduction 'STOE Software' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _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^)+(0.0783P)^2^+0.8843P] 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_number_reflns 4787 _refine_ls_number_parameters 432 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0570 _refine_ls_R_factor_gt 0.0481 _refine_ls_wR_factor_ref 0.1316 _refine_ls_wR_factor_gt 0.1275 _refine_ls_goodness_of_fit_ref 1.035 _refine_ls_restrained_S_all 1.035 _refine_ls_shift/su_max 0.050 _refine_ls_shift/su_mean 0.002 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 0.17384(3) 0.91183(3) 0.22602(3) 0.02232(15) Uani 1 1 d . . . C1 C 0.30852(14) 1.12365(16) 0.08451(12) 0.0335(4) Uani 1 1 d . . . C2 C 0.3006(2) 1.1192(2) -0.01311(15) 0.0553(6) Uani 1 1 d . . . H2A H 0.345(3) 1.058(3) -0.028(3) 0.114(13) Uiso 1 1 d . . . H2B H 0.218(3) 1.117(3) -0.048(2) 0.081(9) Uiso 1 1 d . . . C3 C 0.3337(3) 1.2337(3) -0.0343(2) 0.0724(9) Uani 1 1 d . . . H3A H 0.403(3) 1.208(3) -0.018(2) 0.086(11) Uiso 1 1 d . . . H3B H 0.301(2) 1.253(3) -0.100(2) 0.085(9) Uiso 1 1 d . . . C4 C 0.2913(4) 1.3087(3) 0.0188(3) 0.0911(11) Uani 1 1 d . . . H4A H 0.202(5) 1.286(5) -0.005(4) 0.17(2) Uiso 1 1 d . . . H4B H 0.330(4) 1.386(4) 0.036(3) 0.146(16) Uiso 1 1 d . . . C5 C 0.3163(2) 1.25041(18) 0.10679(18) 0.0560(6) Uani 1 1 d . . . C6 C 0.4314(3) 1.2666(3) 0.1660(2) 0.0775(9) Uani 1 1 d . . . H6A H 0.482(3) 1.251(3) 0.129(2) 0.084(9) Uiso 1 1 d . . . H6B H 0.438(3) 1.341(3) 0.206(2) 0.087(9) Uiso 1 1 d . . . C7 C 0.45817(18) 1.1611(3) 0.21397(15) 0.0616(7) Uani 1 1 d . . . O1 O 0.50885(18) 1.1497(3) 0.28953(12) 0.1107(10) Uani 1 1 d . . . C8 C 0.40866(14) 1.06679(17) 0.15131(12) 0.0379(4) Uani 1 1 d . . . C9 C 0.36636(16) 0.97685(18) 0.19693(15) 0.0410(5) Uani 1 1 d . . . H9A H 0.418(2) 0.966(2) 0.2609(18) 0.062(7) Uiso 1 1 d . . . H9B H 0.359(2) 0.903(2) 0.1636(18) 0.067(8) Uiso 1 1 d . . . C10 C 0.25642(13) 1.01750(13) 0.19296(11) 0.0253(3) Uani 1 1 d . . . H10 H 0.2634(17) 1.0953(17) 0.2328(14) 0.039(5) Uiso 1 1 d . . . C11 C 0.21730(14) 1.05934(17) 0.09903(12) 0.0334(4) Uani 1 1 d . . . H11A H 0.158(2) 1.100(2) 0.0871(16) 0.051(7) Uiso 1 1 d . . . H11B H 0.2004(19) 0.993(2) 0.0588(17) 0.056(7) Uiso 1 1 d . . . C12 C 0.2435(4) 1.2918(2) 0.1560(3) 0.0844(11) Uani 1 1 d . . . H12A H 0.271(3) 1.368(4) 0.172(3) 0.117(13) Uiso 1 1 d . . . H12B H 0.274(3) 1.256(4) 0.214(3) 0.123(14) Uiso 1 1 d . . . H12C H 0.158(6) 1.298(5) 0.107(5) 0.22(3) Uiso 1 1 d . . . C13 C 0.4926(2) 1.0220(3) 0.1156(2) 0.0651(8) Uani 1 1 d . . . H13A H 0.558(3) 0.993(3) 0.170(2) 0.092(10) Uiso 1 1 d . . . H13B H 0.521(3) 1.074(3) 0.092(2) 0.097(11) Uiso 1 1 d . . . H13C H 0.459(3) 0.966(3) 0.075(2) 0.091(12) Uiso 1 1 d . . . C14 C 0.04547(14) 0.97429(14) 0.23156(12) 0.0314(4) Uani 1 1 d . . . C15 C -0.0235(2) 0.8840(2) 0.2506(2) 0.0548(6) Uani 1 1 d . . . H15A H -0.084(3) 0.915(2) 0.2597(19) 0.075(9) Uiso 1 1 d . . . H15B H 0.016(2) 0.851(2) 0.3045(17) 0.054(7) Uiso 1 1 d . . . H15C H -0.047(2) 0.829(3) 0.202(2) 0.074(9) Uiso 1 1 d . . . C16 C -0.01907(17) 1.0338(2) 0.14744(16) 0.0435(5) Uani 1 1 d . . . H16A H -0.031(2) 0.992(3) 0.097(2) 0.073(9) Uiso 1 1 d . . . H16B H 0.017(2) 1.097(2) 0.1386(18) 0.067(8) Uiso 1 1 d . . . H16C H -0.090(2) 1.052(2) 0.1535(16) 0.055(7) Uiso 1 1 d . . . C17 C 0.0735(2) 1.0586(2) 0.30573(16) 0.0507(6) Uani 1 1 d . . . H17A H 0.120(2) 1.122(2) 0.2955(17) 0.067(8) Uiso 1 1 d . . . H17B H 0.112(2) 1.023(2) 0.364(2) 0.074(9) Uiso 1 1 d . . . H17C H 0.007(2) 1.092(2) 0.3102(16) 0.055(7) Uiso 1 1 d . . . C18 C 0.15184(13) 0.78894(13) 0.15132(11) 0.0272(4) Uani 1 1 d . . . C19 C 0.06396(17) 0.77332(19) 0.07681(13) 0.0427(5) Uani 1 1 d . . . H19 H 0.013(2) 0.827(2) 0.0596(16) 0.050(6) Uiso 1 1 d . . . C20 C 0.0540(2) 0.6795(2) 0.02543(15) 0.0572(6) Uani 1 1 d . . . H20 H -0.014(2) 0.670(2) -0.0252(19) 0.070(8) Uiso 1 1 d . . . C21 C 0.1303(2) 0.60025(18) 0.04662(16) 0.0527(6) Uani 1 1 d . . . H21 H 0.124(2) 0.538(2) 0.0121(18) 0.066(8) Uiso 1 1 d . . . C22 C 0.2188(2) 0.61380(17) 0.11820(16) 0.0487(5) Uani 1 1 d . . . H22 H 0.276(2) 0.557(2) 0.1360(17) 0.062(7) Uiso 1 1 d . . . C23 C 0.22927(16) 0.70732(15) 0.16966(13) 0.0377(4) Uani 1 1 d . . . H23 H 0.301(2) 0.722(2) 0.2215(16) 0.056(7) Uiso 1 1 d . . . C24 C 0.25274(13) 0.86177(13) 0.33842(11) 0.0260(3) Uani 1 1 d . . . C25 C 0.33211(14) 0.92432(15) 0.39781(12) 0.0310(4) Uani 1 1 d . . . H25 H 0.3464(16) 0.9930(19) 0.3820(14) 0.037(5) Uiso 1 1 d . . . C26 C 0.38703(16) 0.88641(17) 0.48056(12) 0.0367(4) Uani 1 1 d . . . H26 H 0.4366(19) 0.930(2) 0.5165(16) 0.050(6) Uiso 1 1 d . . . C27 C 0.36479(16) 0.78387(17) 0.50714(13) 0.0392(4) Uani 1 1 d . . . H27 H 0.4039(18) 0.7577(19) 0.5640(16) 0.048(6) Uiso 1 1 d . . . C28 C 0.28691(17) 0.72048(17) 0.45032(13) 0.0419(5) Uani 1 1 d . . . H28 H 0.270(2) 0.651(2) 0.4652(17) 0.064(7) Uiso 1 1 d . . . C29 C 0.23197(16) 0.75852(15) 0.36751(13) 0.0355(4) Uani 1 1 d . . . H29 H 0.1802(17) 0.7163(18) 0.3283(14) 0.040(6) Uiso 1 1 d . . . 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 0.0249(2) 0.0186(2) 0.0234(2) 0.00126(16) 0.00794(17) -0.00087(16) C1 0.0308(9) 0.0374(10) 0.0290(9) 0.0062(8) 0.0056(7) -0.0101(7) C2 0.0565(14) 0.0737(17) 0.0331(11) 0.0107(11) 0.0114(10) -0.0198(13) C3 0.080(2) 0.086(2) 0.0555(16) 0.0280(15) 0.0283(15) -0.0188(17) C4 0.130(3) 0.0592(18) 0.100(3) 0.0364(18) 0.060(2) -0.0002(19) C5 0.0696(15) 0.0330(11) 0.0740(16) 0.0094(10) 0.0353(13) -0.0061(10) C6 0.088(2) 0.0677(18) 0.084(2) -0.0254(16) 0.0370(17) -0.0474(16) C7 0.0385(12) 0.102(2) 0.0408(13) -0.0096(13) 0.0091(10) -0.0351(13) O1 0.0757(14) 0.196(3) 0.0398(11) -0.0085(14) -0.0086(9) -0.0636(16) C8 0.0301(9) 0.0496(11) 0.0339(10) 0.0081(9) 0.0104(8) -0.0009(8) C9 0.0357(10) 0.0466(12) 0.0443(12) 0.0161(9) 0.0179(9) 0.0093(9) C10 0.0257(8) 0.0233(8) 0.0260(8) 0.0028(6) 0.0074(6) -0.0015(6) C11 0.0273(9) 0.0377(10) 0.0308(9) 0.0091(8) 0.0039(7) -0.0074(8) C12 0.126(3) 0.0369(14) 0.116(3) 0.0126(16) 0.074(3) 0.0164(16) C13 0.0579(16) 0.081(2) 0.0715(19) 0.0224(17) 0.0417(15) 0.0146(15) C14 0.0311(9) 0.0290(9) 0.0370(10) 0.0007(7) 0.0150(8) 0.0029(7) C15 0.0435(13) 0.0502(13) 0.0845(19) 0.0155(14) 0.0397(14) 0.0030(11) C16 0.0350(11) 0.0441(12) 0.0488(13) 0.0064(10) 0.0107(9) 0.0140(9) C17 0.0562(13) 0.0485(13) 0.0505(14) -0.0117(11) 0.0222(11) 0.0134(11) C18 0.0325(9) 0.0235(8) 0.0277(8) 0.0002(7) 0.0128(7) -0.0043(7) C19 0.0436(11) 0.0457(11) 0.0335(10) -0.0067(9) 0.0057(9) 0.0022(9) C20 0.0608(14) 0.0663(15) 0.0381(12) -0.0224(11) 0.0079(11) -0.0150(12) C21 0.0776(17) 0.0361(11) 0.0524(13) -0.0201(10) 0.0324(13) -0.0153(11) C22 0.0672(15) 0.0298(10) 0.0548(13) -0.0067(9) 0.0280(12) 0.0018(10) C23 0.0444(11) 0.0280(9) 0.0404(11) -0.0028(8) 0.0137(9) 0.0031(8) C24 0.0292(8) 0.0235(8) 0.0260(8) 0.0020(7) 0.0103(7) -0.0002(6) C25 0.0364(9) 0.0266(9) 0.0302(9) 0.0007(7) 0.0115(7) -0.0032(7) C26 0.0364(10) 0.0412(10) 0.0286(9) -0.0038(8) 0.0055(8) -0.0036(8) C27 0.0443(11) 0.0441(11) 0.0265(9) 0.0088(8) 0.0084(8) 0.0077(9) C28 0.0550(12) 0.0331(10) 0.0363(10) 0.0115(8) 0.0133(9) -0.0018(9) C29 0.0415(10) 0.0288(9) 0.0322(10) 0.0047(8) 0.0071(8) -0.0070(8) _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 C24 1.8818(17) . ? Si1 C18 1.8861(17) . ? Si1 C10 1.8874(16) . ? Si1 C14 1.9107(18) . ? C1 C11 1.535(2) . ? C1 C2 1.555(3) . ? C1 C8 1.578(3) . ? C1 C5 1.579(3) . ? C2 C3 1.536(4) . ? C3 C4 1.493(5) . ? C4 C5 1.529(4) . ? C5 C6 1.536(4) . ? C5 C12 1.537(4) . ? C6 C7 1.483(4) . ? C7 O1 1.197(3) . ? C7 C8 1.531(3) . ? C8 C13 1.527(3) . ? C8 C9 1.532(3) . ? C9 C10 1.536(2) . ? C10 C11 1.527(2) . ? C14 C17 1.531(3) . ? C14 C15 1.533(3) . ? C14 C16 1.535(3) . ? C18 C19 1.394(3) . ? C18 C23 1.395(3) . ? C19 C20 1.395(3) . ? C20 C21 1.364(4) . ? C21 C22 1.368(4) . ? C22 C23 1.391(3) . ? C24 C25 1.400(2) . ? C24 C29 1.402(2) . ? C25 C26 1.380(3) . ? C26 C27 1.385(3) . ? C27 C28 1.377(3) . ? C28 C29 1.381(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 C24 Si1 C18 106.58(7) . . ? C24 Si1 C10 107.64(7) . . ? C18 Si1 C10 109.74(7) . . ? C24 Si1 C14 107.91(8) . . ? C18 Si1 C14 113.26(8) . . ? C10 Si1 C14 111.43(8) . . ? C11 C1 C2 110.58(16) . . ? C11 C1 C8 102.13(14) . . ? C2 C1 C8 116.11(18) . . ? C11 C1 C5 117.26(17) . . ? C2 C1 C5 104.17(18) . . ? C8 C1 C5 107.08(16) . . ? C3 C2 C1 105.7(2) . . ? C4 C3 C2 103.3(2) . . ? C3 C4 C5 104.4(3) . . ? C4 C5 C6 112.9(3) . . ? C4 C5 C12 110.7(3) . . ? C6 C5 C12 108.2(3) . . ? C4 C5 C1 105.2(2) . . ? C6 C5 C1 104.2(2) . . ? C12 C5 C1 115.7(2) . . ? C7 C6 C5 103.61(19) . . ? O1 C7 C6 126.5(3) . . ? O1 C7 C8 124.6(3) . . ? C6 C7 C8 108.9(2) . . ? C13 C8 C7 108.0(2) . . ? C13 C8 C9 111.5(2) . . ? C7 C8 C9 111.19(18) . . ? C13 C8 C1 117.45(19) . . ? C7 C8 C1 102.17(18) . . ? C9 C8 C1 106.18(15) . . ? C8 C9 C10 104.72(15) . . ? C11 C10 C9 98.93(14) . . ? C11 C10 Si1 118.20(12) . . ? C9 C10 Si1 114.48(12) . . ? C10 C11 C1 107.28(14) . . ? C17 C14 C15 109.2(2) . . ? C17 C14 C16 107.66(17) . . ? C15 C14 C16 108.59(19) . . ? C17 C14 Si1 108.29(14) . . ? C15 C14 Si1 109.74(13) . . ? C16 C14 Si1 113.31(13) . . ? C19 C18 C23 116.27(17) . . ? C19 C18 Si1 124.99(14) . . ? C23 C18 Si1 118.72(14) . . ? C18 C19 C20 121.1(2) . . ? C21 C20 C19 120.9(2) . . ? C20 C21 C22 119.7(2) . . ? C21 C22 C23 119.7(2) . . ? C22 C23 C18 122.3(2) . . ? C25 C24 C29 116.43(16) . . ? C25 C24 Si1 123.12(13) . . ? C29 C24 Si1 120.44(13) . . ? C26 C25 C24 121.81(17) . . ? C25 C26 C27 120.30(18) . . ? C28 C27 C26 119.29(18) . . ? C27 C28 C29 120.36(18) . . ? C28 C29 C24 121.81(18) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.85 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.424 _refine_diff_density_min -0.193 _refine_diff_density_rms 0.044