# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is (c) The Royal Society of Chemistry 2009 data_global #=============================================================================== # 1. SUBMISSION DETAILS _publ_contact_authors ; Prof. P.-Q. Huang Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. China Fax: (+) 86-592-2186400 ; _publ_contact_author_phone '0086-592-2182240' _publ_contact_author_email pqhuang@xmu.edu.cn _publ_requested_journal 'The Journal of Organic Chemistry' #=============================================================================== # 2. TITLE AND AUTHOR LIST _publ_section_title ; A Concise and Highly Diastereoselective Synthesis of the Ant Venom Alkaloid (3S,5R,8S,9S)-3-Butyl-5-propyl-8-hydroxyindolizidine ; loop_ _publ_author_name 'Lin, GengJie' ; Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. China ; 'Huang, PeiQiang' ; Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. China ; #=============================================== data_a _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H31 N O4' _chemical_formula_weight 325.44 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 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, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _chemical_absolute_configuration 'rm' _cell_length_a 5.5694(15) _cell_length_b 10.414(3) _cell_length_c 30.935(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1794.2(8) _cell_formula_units_Z 4 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description 'needle' _exptl_crystal_colour 'colourless' _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.205 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 712 _exptl_absorpt_coefficient_mu 0.084 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.9637 _exptl_absorpt_correction_T_max 0.9839 _exptl_absorpt_process_details 'SADABS (Sheldrick, 1996)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(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 'Bruker AXS area-detector diffractometer' _diffrn_measurement_method '\f and \w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15354 _diffrn_reflns_av_R_equivalents 0.0503 _diffrn_reflns_av_sigmaI/netI 0.0553 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -40 _diffrn_reflns_limit_l_max 40 _diffrn_reflns_theta_min 1.32 _diffrn_reflns_theta_max 28.33 _reflns_number_total 4233 _reflns_number_gt 2953 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _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^)+(0.1000P)^2^+0.0000P] 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 contr _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 -0.6(15) _refine_ls_number_reflns 4233 _refine_ls_number_parameters 208 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0884 _refine_ls_R_factor_gt 0.0569 _refine_ls_wR_factor_ref 0.1660 _refine_ls_wR_factor_gt 0.1508 _refine_ls_goodness_of_fit_ref 1.024 _refine_ls_restrained_S_all 1.024 _refine_ls_shift/su_max 0.043 _refine_ls_shift/su_mean 0.004 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 O3 O 0.3915(3) 0.21612(17) 0.12636(6) 0.0379(4) Uani 1 1 d . . . O1 O -0.0744(3) 0.29814(15) 0.24554(5) 0.0354(4) Uani 1 1 d . . . O4 O 0.0711(3) 0.12990(16) 0.09066(6) 0.0354(4) Uani 1 1 d . . . O2 O -0.0812(4) 0.35720(17) 0.31484(6) 0.0457(5) Uani 1 1 d . . . N1 N -0.2024(4) 0.15536(19) 0.29355(6) 0.0284(5) Uani 1 1 d . . . C6 C -0.1839(5) 0.1974(2) 0.21973(8) 0.0308(6) Uani 1 1 d . . . H6A H -0.3417 0.2255 0.2094 0.037 Uiso 1 1 calc R . . C7 C -0.1217(5) 0.2770(2) 0.28811(7) 0.0312(5) Uani 1 1 d . . . C8 C -0.2137(5) 0.0877(2) 0.25195(7) 0.0313(5) Uani 1 1 d . . . H8A H -0.0780 0.0282 0.2495 0.038 Uiso 1 1 calc R . . C9 C -0.0243(5) 0.1679(2) 0.18197(8) 0.0320(5) Uani 1 1 d . . . H9A H -0.0845 0.0917 0.1676 0.038 Uiso 1 1 calc R . . H9B H 0.1353 0.1485 0.1927 0.038 Uiso 1 1 calc R . . C10 C 0.1633(5) 0.3525(3) 0.07877(8) 0.0394(6) Uani 1 1 d . . . H10A H 0.2167 0.4294 0.0936 0.047 Uiso 1 1 calc R . . H10B H 0.0015 0.3684 0.0685 0.047 Uiso 1 1 calc R . . C11 C 0.1549(4) 0.2435(2) 0.11112(7) 0.0316(6) Uani 1 1 d . . . C12 C -0.0060(5) 0.2752(2) 0.14923(8) 0.0323(5) Uani 1 1 d . . . H12A H 0.0555 0.3513 0.1635 0.039 Uiso 1 1 calc R . . H12B H -0.1655 0.2950 0.1386 0.039 Uiso 1 1 calc R . . C13 C -0.6731(5) 0.1645(3) 0.38470(8) 0.0395(6) Uani 1 1 d . . . H13A H -0.8148 0.1374 0.3689 0.047 Uiso 1 1 calc R . . H13B H -0.6089 0.0898 0.3994 0.047 Uiso 1 1 calc R . . C14 C -0.3925(5) 0.1123(2) 0.32283(8) 0.0337(6) Uani 1 1 d . . . H14A H -0.3344 0.0390 0.3397 0.040 Uiso 1 1 calc R . . C15 C -0.4892(5) 0.2126(3) 0.35296(9) 0.0404(6) Uani 1 1 d . . . H15A H -0.5608 0.2807 0.3359 0.049 Uiso 1 1 calc R . . H15B H -0.3563 0.2495 0.3690 0.049 Uiso 1 1 calc R . . C16 C 0.3248(6) 0.3311(3) 0.03986(9) 0.0502(8) Uani 1 1 d . . . H16A H 0.4873 0.3146 0.0497 0.060 Uiso 1 1 calc R . . H16B H 0.2701 0.2560 0.0242 0.060 Uiso 1 1 calc R . . C17 C -0.4465(6) 0.0133(3) 0.25293(9) 0.0461(7) Uani 1 1 d . . . H17A H -0.5353 0.0256 0.2263 0.055 Uiso 1 1 calc R . . H17B H -0.4160 -0.0777 0.2568 0.055 Uiso 1 1 calc R . . C18 C -0.7455(6) 0.2620(3) 0.41778(10) 0.0557(9) Uani 1 1 d . . . H18A H -0.8114 0.3362 0.4030 0.067 Uiso 1 1 calc R . . H18B H -0.6031 0.2900 0.4332 0.067 Uiso 1 1 calc R . . C19 C -0.5806(6) 0.0651(4) 0.28982(11) 0.0650(10) Uani 1 1 d . . . H19A H -0.6810 -0.0009 0.3025 0.078 Uiso 1 1 calc R . . H19B H -0.6823 0.1357 0.2807 0.078 Uiso 1 1 calc R . . C20 C -0.9264(7) 0.2154(3) 0.45014(11) 0.0614(9) Uani 1 1 d . . . H20A H -0.9627 0.2832 0.4701 0.092 Uiso 1 1 calc R . . H20B H -0.8618 0.1433 0.4656 0.092 Uiso 1 1 calc R . . H20C H -1.0704 0.1899 0.4354 0.092 Uiso 1 1 calc R . . C22 C 0.4508(6) 0.0876(3) 0.11584(12) 0.0539(8) Uani 1 1 d . . . H22A H 0.4717 0.0372 0.1419 0.065 Uiso 1 1 calc R . . H22B H 0.5989 0.0848 0.0994 0.065 Uiso 1 1 calc R . . C21 C 0.2523(6) 0.0372(3) 0.09022(12) 0.0546(8) Uani 1 1 d . . . H21A H 0.3043 0.0207 0.0608 0.066 Uiso 1 1 calc R . . H21B H 0.1942 -0.0426 0.1026 0.066 Uiso 1 1 calc R . . C23 C 0.3257(8) 0.4455(3) 0.00985(10) 0.0663(10) Uani 1 1 d . . . H23A H 0.4273 0.4278 -0.0145 0.099 Uiso 1 1 calc R . . H23B H 0.3852 0.5194 0.0250 0.099 Uiso 1 1 calc R . . H23C H 0.1652 0.4620 0.0000 0.099 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 O3 0.0284(10) 0.0435(10) 0.0420(9) -0.0056(9) -0.0034(8) -0.0036(9) O1 0.0472(10) 0.0253(9) 0.0339(9) -0.0012(7) 0.0059(8) -0.0044(8) O4 0.0336(9) 0.0354(9) 0.0374(9) -0.0069(8) -0.0034(7) -0.0011(8) O2 0.0605(13) 0.0339(9) 0.0429(10) -0.0141(9) 0.0069(9) -0.0119(10) N1 0.0297(11) 0.0271(10) 0.0285(10) -0.0008(9) 0.0016(8) -0.0018(9) C6 0.0318(13) 0.0292(12) 0.0313(12) -0.0013(10) -0.0013(10) 0.0004(10) C7 0.0342(14) 0.0284(12) 0.0311(12) -0.0018(11) 0.0029(10) 0.0001(11) C8 0.0391(14) 0.0296(12) 0.0252(12) -0.0036(10) 0.0021(11) -0.0030(11) C9 0.0342(14) 0.0290(12) 0.0329(12) -0.0005(10) 0.0022(10) -0.0022(11) C10 0.0464(16) 0.0378(14) 0.0341(13) 0.0006(12) 0.0043(12) -0.0004(12) C11 0.0280(13) 0.0355(14) 0.0312(12) -0.0011(10) 0.0023(10) -0.0013(10) C12 0.0349(14) 0.0289(12) 0.0332(12) -0.0002(11) 0.0017(10) -0.0007(11) C13 0.0454(15) 0.0383(14) 0.0347(14) 0.0008(12) 0.0065(12) -0.0004(12) C14 0.0405(15) 0.0288(12) 0.0319(13) 0.0058(10) 0.0069(11) 0.0014(12) C15 0.0480(17) 0.0338(13) 0.0395(14) 0.0009(12) 0.0068(12) -0.0028(13) C16 0.0590(19) 0.0477(17) 0.0438(16) 0.0079(14) 0.0158(15) 0.0002(15) C17 0.0498(18) 0.0497(17) 0.0389(15) 0.0010(13) -0.0013(14) -0.0214(14) C18 0.057(2) 0.0565(19) 0.0541(19) -0.0082(16) 0.0207(15) -0.0076(16) C19 0.0527(19) 0.074(2) 0.069(2) -0.0283(18) 0.0217(18) -0.0280(18) C20 0.066(2) 0.064(2) 0.0540(18) -0.0063(17) 0.0233(16) -0.0023(19) C22 0.0423(17) 0.0510(17) 0.068(2) -0.0162(16) -0.0104(15) 0.0115(15) C21 0.0456(18) 0.0408(16) 0.078(2) -0.0112(16) -0.0088(16) 0.0088(14) C23 0.098(3) 0.056(2) 0.0445(18) 0.0079(15) 0.0281(19) 0.005(2) _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 O3 C22 1.416(3) . ? O3 C11 1.428(3) . ? O1 C7 1.361(3) . ? O1 C6 1.453(3) . ? O4 C21 1.397(3) . ? O4 C11 1.420(3) . ? O2 C7 1.197(3) . ? N1 C7 1.355(3) . ? N1 C14 1.464(3) . ? N1 C8 1.468(3) . ? C6 C9 1.499(3) . ? C6 C8 1.525(3) . ? C8 C17 1.511(4) . ? C9 C12 1.511(3) . ? C10 C11 1.514(4) . ? C10 C16 1.519(4) . ? C11 C12 1.517(3) . ? C13 C18 1.497(4) . ? C13 C15 1.504(4) . ? C14 C15 1.500(4) . ? C14 C19 1.543(4) . ? C16 C23 1.510(4) . ? C17 C19 1.467(4) . ? C18 C20 1.501(4) . ? C22 C21 1.458(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 C22 O3 C11 109.2(2) . . ? C7 O1 C6 109.49(18) . . ? C21 O4 C11 110.0(2) . . ? C7 N1 C14 127.1(2) . . ? C7 N1 C8 110.72(19) . . ? C14 N1 C8 111.37(19) . . ? O1 C6 C9 109.1(2) . . ? O1 C6 C8 103.14(18) . . ? C9 C6 C8 114.9(2) . . ? O2 C7 N1 129.0(2) . . ? O2 C7 O1 121.3(2) . . ? N1 C7 O1 109.6(2) . . ? N1 C8 C17 105.4(2) . . ? N1 C8 C6 102.07(18) . . ? C17 C8 C6 119.4(2) . . ? C6 C9 C12 114.3(2) . . ? C11 C10 C16 115.6(2) . . ? O4 C11 O3 106.5(2) . . ? O4 C11 C10 109.89(19) . . ? O3 C11 C10 109.8(2) . . ? O4 C11 C12 109.47(19) . . ? O3 C11 C12 109.38(19) . . ? C10 C11 C12 111.6(2) . . ? C9 C12 C11 113.6(2) . . ? C18 C13 C15 113.8(2) . . ? N1 C14 C15 115.5(2) . . ? N1 C14 C19 100.3(2) . . ? C15 C14 C19 112.9(2) . . ? C14 C15 C13 114.7(2) . . ? C23 C16 C10 111.9(3) . . ? C19 C17 C8 105.3(2) . . ? C13 C18 C20 114.7(3) . . ? C17 C19 C14 106.6(3) . . ? O3 C22 C21 106.8(2) . . ? O4 C21 C22 107.1(2) . . ? _diffrn_measured_fraction_theta_max 0.972 _diffrn_reflns_theta_full 28.33 _diffrn_measured_fraction_theta_full 0.972 _refine_diff_density_max 0.629 _refine_diff_density_min -0.365 _refine_diff_density_rms 0.050