Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Jincheng Mao' _publ_contact_author_address ; chemical Suzhou(Soochow) University Suzhou 215123 CHINA ; _publ_contact_author_email JCMAO@SUDA.EDU.CN _publ_section_title ; Highly Enantioselective Asymmetric Alkynylation of Aldehydes Catalyzed by a New Oxazolidine-Titanium Complex ; loop_ _publ_author_name 'Jincheng Mao' 'Zhou Xu' 'Ya-Wen Zhang' data_shelxl _database_code_depnum_ccdc_archive 'CCDC 667689' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H15 N O' _chemical_formula_sum 'C16 H15 N O' _chemical_formula_weight 237.29 _chemical_absolute_configuration rm 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' N N 0.0061 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 monoclinic _symmetry_space_group_name_H-M 'C 2' _symmetry_space_group_name_Hall 'C 2y' _symmetry_Int_Tables_number 5 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 19.246(6) _cell_length_b 5.8447(16) _cell_length_c 14.509(5) _cell_angle_alpha 90.00 _cell_angle_beta 129.844(4) _cell_angle_gamma 90.00 _cell_volume 1253.1(7) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 2633 _cell_measurement_theta_min 3.7 _cell_measurement_theta_max 25.3 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.25 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.258 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 504 _exptl_absorpt_coefficient_mu 0.078 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.772 _exptl_absorpt_correction_T_max 0.981 _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication' _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku Mercury' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 7.31 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6058 _diffrn_reflns_av_R_equivalents 0.0222 _diffrn_reflns_av_sigmaI/netI 0.0169 _diffrn_reflns_limit_h_min -22 _diffrn_reflns_limit_h_max 22 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.66 _diffrn_reflns_theta_max 25.34 _reflns_number_total 1252 _reflns_number_gt 1215 _reflns_threshold_expression >2sigma(I) _computing_data_collection CrystalClear _computing_cell_refinement CrystalClear _computing_data_reduction CrystalStructure _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^)+(0.0483P)^2^+0.1815P] 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 0.031(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack (1983), 943 Friedel pairs' _refine_ls_number_reflns 1252 _refine_ls_number_parameters 169 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0330 _refine_ls_R_factor_gt 0.0315 _refine_ls_wR_factor_ref 0.0802 _refine_ls_wR_factor_gt 0.0792 _refine_ls_goodness_of_fit_ref 1.084 _refine_ls_restrained_S_all 1.084 _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 O1 O 0.37312(10) -0.1383(3) -0.03384(12) 0.0515(4) Uani 1 1 d . . . N1 N 0.33282(10) 0.1086(3) 0.04937(14) 0.0469(5) Uani 1 1 d . . . H1A H 0.2761(15) 0.045(5) 0.009(2) 0.063(7) Uiso 1 1 d . . . C1 C 0.35168(12) 0.0953(3) -0.03231(16) 0.0387(5) Uani 1 1 d . . . H1B H 0.4054 0.1907 -0.0003 0.046 Uiso 1 1 calc R . . C2 C 0.41495(14) -0.2351(4) 0.08139(18) 0.0498(5) Uani 1 1 d . . . H2 H 0.3870 -0.3838 0.0736 0.060 Uiso 1 1 calc R . . C3 C 0.39825(13) -0.0562(4) 0.14422(17) 0.0475(5) Uani 1 1 d . . . H3 H 0.3743 -0.1289 0.1804 0.057 Uiso 1 1 calc R . . C4 C 0.51755(14) -0.2597(4) 0.15645(18) 0.0525(6) Uani 1 1 d . . . H4A H 0.5386 -0.4073 0.1981 0.063 Uiso 1 1 calc R . . H4B H 0.5345 -0.2471 0.1057 0.063 Uiso 1 1 calc R . . C5 C 0.55668(12) -0.0661(4) 0.24445(15) 0.0417(5) Uani 1 1 d . . . C6 C 0.64563(13) 0.0088(4) 0.32425(17) 0.0527(6) Uani 1 1 d . . . H6 H 0.6905 -0.0643 0.3271 0.063 Uiso 1 1 calc R . . C7 C 0.66799(14) 0.1896(5) 0.39887(18) 0.0586(6) Uani 1 1 d . . . H7 H 0.7285 0.2382 0.4539 0.070 Uiso 1 1 calc R . . C8 C 0.60316(16) 0.2998(5) 0.39405(18) 0.0617(7) Uani 1 1 d . . . H8 H 0.6194 0.4235 0.4458 0.074 Uiso 1 1 calc R . . C9 C 0.51317(14) 0.2302(5) 0.31309(17) 0.0554(6) Uani 1 1 d . . . H9 H 0.4685 0.3074 0.3091 0.066 Uiso 1 1 calc R . . C10 C 0.49052(12) 0.0468(4) 0.23887(16) 0.0406(5) Uani 1 1 d . . . C11 C 0.27486(12) 0.1727(3) -0.15803(17) 0.0377(4) Uani 1 1 d . . . C12 C 0.20029(12) 0.0322(4) -0.23457(16) 0.0447(5) Uani 1 1 d . . . H12 H 0.1972 -0.1102 -0.2073 0.054 Uiso 1 1 calc R . . C13 C 0.13038(13) 0.1014(4) -0.35121(18) 0.0509(5) Uani 1 1 d . . . H13 H 0.0804 0.0045 -0.4029 0.061 Uiso 1 1 calc R . . C14 C 0.13337(15) 0.3103(4) -0.39214(19) 0.0525(6) Uani 1 1 d . . . H14 H 0.0858 0.3564 -0.4713 0.063 Uiso 1 1 calc R . . C15 C 0.20635(16) 0.4503(5) -0.31637(19) 0.0561(6) Uani 1 1 d . . . H15 H 0.2086 0.5937 -0.3437 0.067 Uiso 1 1 calc R . . C16 C 0.27705(15) 0.3825(4) -0.19966(18) 0.0490(5) Uani 1 1 d . . . H16 H 0.3268 0.4803 -0.1485 0.059 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 0.0543(8) 0.0475(8) 0.0393(7) -0.0041(6) 0.0237(7) 0.0110(7) N1 0.0344(8) 0.0658(12) 0.0403(8) -0.0019(9) 0.0239(7) 0.0039(9) C1 0.0352(9) 0.0401(11) 0.0404(10) -0.0075(9) 0.0240(8) -0.0033(8) C2 0.0491(11) 0.0407(11) 0.0483(11) 0.0003(10) 0.0260(9) -0.0064(10) C3 0.0403(10) 0.0625(13) 0.0438(10) 0.0053(10) 0.0289(9) -0.0036(10) C4 0.0533(12) 0.0481(13) 0.0457(11) 0.0053(10) 0.0269(10) 0.0114(11) C5 0.0423(10) 0.0495(12) 0.0338(9) 0.0077(9) 0.0247(8) 0.0058(9) C6 0.0360(10) 0.0779(17) 0.0392(10) 0.0097(11) 0.0218(9) 0.0078(10) C7 0.0413(10) 0.0787(17) 0.0386(11) 0.0000(11) 0.0177(9) -0.0092(11) C8 0.0640(14) 0.0653(17) 0.0389(11) -0.0072(11) 0.0252(11) -0.0047(13) C9 0.0496(12) 0.0722(16) 0.0428(11) -0.0023(11) 0.0289(10) 0.0096(12) C10 0.0390(9) 0.0517(12) 0.0334(9) 0.0044(9) 0.0243(8) 0.0007(9) C11 0.0383(9) 0.0381(11) 0.0406(9) -0.0052(8) 0.0270(8) -0.0008(8) C12 0.0389(10) 0.0443(12) 0.0430(10) 0.0013(9) 0.0227(9) -0.0056(9) C13 0.0389(10) 0.0599(13) 0.0417(10) -0.0001(10) 0.0202(9) -0.0060(11) C14 0.0528(12) 0.0571(15) 0.0429(11) 0.0084(10) 0.0285(10) 0.0111(11) C15 0.0766(15) 0.0401(11) 0.0547(12) 0.0052(11) 0.0435(12) 0.0020(12) C16 0.0573(12) 0.0413(12) 0.0494(11) -0.0096(10) 0.0346(11) -0.0108(10) _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 C2 1.428(3) . ? O1 C1 1.431(3) . ? N1 C1 1.447(2) . ? N1 C3 1.478(3) . ? N1 H1A 0.92(2) . ? C1 C11 1.504(3) . ? C1 H1B 0.9900 . ? C2 C4 1.533(3) . ? C2 C3 1.550(3) . ? C2 H2 0.9900 . ? C3 C10 1.509(3) . ? C3 H3 0.9900 . ? C4 C5 1.499(3) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C5 C6 1.387(3) . ? C5 C10 1.390(3) . ? C6 C7 1.370(4) . ? C6 H6 0.9400 . ? C7 C8 1.366(3) . ? C7 H7 0.9400 . ? C8 C9 1.392(3) . ? C8 H8 0.9400 . ? C9 C10 1.377(3) . ? C9 H9 0.9400 . ? C11 C16 1.380(3) . ? C11 C12 1.387(3) . ? C12 C13 1.386(3) . ? C12 H12 0.9400 . ? C13 C14 1.375(3) . ? C13 H13 0.9400 . ? C14 C15 1.368(3) . ? C14 H14 0.9400 . ? C15 C16 1.387(3) . ? C15 H15 0.9400 . ? C16 H16 0.9400 . ? 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 C2 O1 C1 108.16(16) . . ? C1 N1 C3 102.51(14) . . ? C1 N1 H1A 105.6(15) . . ? C3 N1 H1A 106.6(17) . . ? O1 C1 N1 106.85(17) . . ? O1 C1 C11 109.71(15) . . ? N1 C1 C11 114.19(14) . . ? O1 C1 H1B 108.7 . . ? N1 C1 H1B 108.7 . . ? C11 C1 H1B 108.7 . . ? O1 C2 C4 111.85(18) . . ? O1 C2 C3 104.34(17) . . ? C4 C2 C3 107.66(17) . . ? O1 C2 H2 110.9 . . ? C4 C2 H2 110.9 . . ? C3 C2 H2 110.9 . . ? N1 C3 C10 113.03(19) . . ? N1 C3 C2 105.41(15) . . ? C10 C3 C2 103.76(15) . . ? N1 C3 H3 111.4 . . ? C10 C3 H3 111.4 . . ? C2 C3 H3 111.4 . . ? C5 C4 C2 104.48(18) . . ? C5 C4 H4A 110.9 . . ? C2 C4 H4A 110.9 . . ? C5 C4 H4B 110.9 . . ? C2 C4 H4B 110.9 . . ? H4A C4 H4B 108.9 . . ? C6 C5 C10 119.6(2) . . ? C6 C5 C4 128.87(19) . . ? C10 C5 C4 111.55(18) . . ? C7 C6 C5 119.9(2) . . ? C7 C6 H6 120.1 . . ? C5 C6 H6 120.1 . . ? C8 C7 C6 120.6(2) . . ? C8 C7 H7 119.7 . . ? C6 C7 H7 119.7 . . ? C7 C8 C9 120.5(2) . . ? C7 C8 H8 119.7 . . ? C9 C8 H8 119.8 . . ? C10 C9 C8 119.1(2) . . ? C10 C9 H9 120.4 . . ? C8 C9 H9 120.4 . . ? C9 C10 C5 120.31(19) . . ? C9 C10 C3 128.35(18) . . ? C5 C10 C3 111.33(19) . . ? C16 C11 C12 118.80(18) . . ? C16 C11 C1 121.07(17) . . ? C12 C11 C1 120.13(17) . . ? C13 C12 C11 120.1(2) . . ? C13 C12 H12 119.9 . . ? C11 C12 H12 119.9 . . ? C14 C13 C12 120.7(2) . . ? C14 C13 H13 119.7 . . ? C12 C13 H13 119.7 . . ? C15 C14 C13 119.3(2) . . ? C15 C14 H14 120.3 . . ? C13 C14 H14 120.3 . . ? C14 C15 C16 120.6(2) . . ? C14 C15 H15 119.7 . . ? C16 C15 H15 119.7 . . ? C11 C16 C15 120.5(2) . . ? C11 C16 H16 119.8 . . ? C15 C16 H16 119.8 . . ? 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 C2 O1 C1 N1 -31.03(19) . . . . ? C2 O1 C1 C11 -155.31(15) . . . . ? C3 N1 C1 O1 36.41(19) . . . . ? C3 N1 C1 C11 157.90(17) . . . . ? C1 O1 C2 C4 -104.1(2) . . . . ? C1 O1 C2 C3 11.96(19) . . . . ? C1 N1 C3 C10 84.60(19) . . . . ? C1 N1 C3 C2 -28.1(2) . . . . ? O1 C2 C3 N1 10.4(2) . . . . ? C4 C2 C3 N1 129.39(18) . . . . ? O1 C2 C3 C10 -108.63(17) . . . . ? C4 C2 C3 C10 10.4(2) . . . . ? O1 C2 C4 C5 103.13(19) . . . . ? C3 C2 C4 C5 -10.9(2) . . . . ? C2 C4 C5 C6 -171.6(2) . . . . ? C2 C4 C5 C10 7.5(2) . . . . ? C10 C5 C6 C7 1.6(3) . . . . ? C4 C5 C6 C7 -179.3(2) . . . . ? C5 C6 C7 C8 -1.2(3) . . . . ? C6 C7 C8 C9 0.0(4) . . . . ? C7 C8 C9 C10 0.8(4) . . . . ? C8 C9 C10 C5 -0.4(3) . . . . ? C8 C9 C10 C3 -179.3(2) . . . . ? C6 C5 C10 C9 -0.8(3) . . . . ? C4 C5 C10 C9 179.97(19) . . . . ? C6 C5 C10 C3 178.26(17) . . . . ? C4 C5 C10 C3 -1.0(2) . . . . ? N1 C3 C10 C9 59.4(3) . . . . ? C2 C3 C10 C9 173.0(2) . . . . ? N1 C3 C10 C5 -119.58(18) . . . . ? C2 C3 C10 C5 -5.9(2) . . . . ? O1 C1 C11 C16 -135.75(18) . . . . ? N1 C1 C11 C16 104.3(2) . . . . ? O1 C1 C11 C12 44.0(2) . . . . ? N1 C1 C11 C12 -75.9(2) . . . . ? C16 C11 C12 C13 1.1(3) . . . . ? C1 C11 C12 C13 -178.63(17) . . . . ? C11 C12 C13 C14 -0.8(3) . . . . ? C12 C13 C14 C15 0.0(3) . . . . ? C13 C14 C15 C16 0.4(3) . . . . ? C12 C11 C16 C15 -0.7(3) . . . . ? C1 C11 C16 C15 179.04(18) . . . . ? C14 C15 C16 C11 -0.1(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 C16 H16 O1 0.94 2.58 3.369(3) 142.3 1_565 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 25.34 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.116 _refine_diff_density_min -0.096 _refine_diff_density_rms 0.024