Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_5g _database_code_CSD 156841 _journal_coden_Cambridge 182 _publ_requested_journal 'Chem. Commun.' loop_ _publ_author_name 'So Won Youn' 'Yong Hae Kim' 'Jeong-Wook Hwang' 'Youngkyu Do' _publ_contact_author 'Prof Yong Hae Kim' _publ_contact_author_email 'kimyh@mail.kaist.ac.kr' _publ_contact_author_address ; Prof Yong Hae Kim Center for Molecular Design & Synthesis, Department of Chemistry, Korea Advanced Institute of Science and Technology, Taejon, 305-701 KOREA ; _publ_section_title ; Highly diastereoselective additions of methoxyallene and acetylenes to chiral alpha-keto amides ; _publ_requested_journal 'Chem. Commun.' _audit_creation_method SHELXL _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C15 H17 N O3' _chemical_formula_weight 259.30 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'O' 'O' 0.0106 0.0060 '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' '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' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M P212121 (No. 19) 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' _cell_length_a 10.300(2) _cell_length_b 10.536(2) _cell_length_c 25.810(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2800.9(11) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 0 _cell_measurement_theta_min 0.0 _cell_measurement_theta_max 0.0 _exptl_crystal_description 'rectangular block' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max '0.22 mm' _exptl_crystal_size_mid '0.15 mm' _exptl_crystal_size_min '0.12 mm' _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_diffrn 1.230 _exptl_crystal_F_000 1104 _exptl_absorpt_coefficient_mu 0.086 _exptl_absorpt_correction_type 'SADABS-Bruker area detector absortion corrections' _exptl_absorpt_correction_T_min 0.7411 _exptl_absorpt_correction_T_max 1.0000 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Bruker SMART 1K CCD' _diffrn_measurement_method scanning _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 32006 _diffrn_reflns_av_R_equivalents 0.0814 _diffrn_reflns_av_sigmaI/netI 0.1353 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -34 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 1.58 _diffrn_reflns_theta_max 28.09 _reflns_number_total 6530 _reflns_number_observed 2661 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'SMART' _computing_cell_refinement 'SMART' _computing_data_reduction 'SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'ORTEP' _computing_publication_material 'SHELXL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 0 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w==1/[\s^2^(Fo^2^)+(0.0126P)^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 'refined isotropically' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0062(2) _refine_ls_extinction_expression 'Fc^*^==kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.43(76) _refine_ls_number_reflns 6530 _refine_ls_number_parameters 480 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1345 _refine_ls_R_factor_obs 0.0333 _refine_ls_wR_factor_all 0.0502 _refine_ls_wR_factor_obs 0.0404 _refine_ls_goodness_of_fit_all 0.713 _refine_ls_goodness_of_fit_obs 0.956 _refine_ls_restrained_S_all 0.713 _refine_ls_restrained_S_obs 0.956 _refine_ls_shift/esd_max -0.003 _refine_ls_shift/esd_mean 0.001 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group C1 C -0.0199(2) 0.3381(2) 0.51079(9) 0.0442(6) Uani 1 d . . H1 H -0.0609(15) 0.3937(14) 0.4830(6) 0.038(6) Uiso 1 d . . N1 N 0.0024(2) 0.2063(2) 0.49070(7) 0.0451(5) Uani 1 d . . O1 O 0.08650(14) 0.52502(13) 0.53741(5) 0.0543(4) Uani 1 d . . C2 C -0.1084(2) 0.3153(2) 0.55770(9) 0.0535(7) Uani 1 d . . H2A H -0.0919(18) 0.3894(16) 0.5858(7) 0.063(6) Uiso 1 d . . H2B H -0.2048(17) 0.3253(15) 0.5452(7) 0.055(6) Uiso 1 d . . O2 O 0.0144(2) 0.05401(15) 0.42997(5) 0.0678(5) Uani 1 d . . C3 C -0.0739(2) 0.1824(2) 0.57375(9) 0.0515(6) Uani 1 d . . H3 H 0.0909(23) 0.4257(22) 0.3917(8) 0.084(10) Uiso 1 d . . O3 O 0.0963(2) 0.3643(2) 0.41145(6) 0.0559(5) Uani 1 d . . C4 C -0.0971(2) 0.1183(3) 0.61980(10) 0.0608(7) Uani 1 d . . H4 H -0.1438(18) 0.1630(17) 0.6479(7) 0.062(7) Uiso 1 d . . C5 C -0.0557(3) -0.0044(3) 0.62508(12) 0.0718(8) Uani 1 d . . H5 H -0.0719(20) -0.0515(20) 0.6582(8) 0.078(8) Uiso 1 d . . C6 C 0.0052(3) -0.0641(3) 0.58474(13) 0.0720(9) Uani 1 d . . H6 H 0.0311(20) -0.1434(19) 0.5873(8) 0.075(9) Uiso 1 d . . C7 C 0.0306(2) -0.0036(2) 0.53760(11) 0.0615(7) Uani 1 d . . H7 H 0.0859(23) -0.0437(22) 0.5079(8) 0.101(10) Uiso 1 d . . C8 C -0.0121(2) 0.1209(2) 0.53358(8) 0.0477(6) Uani 1 d . . C9 C 0.1089(2) 0.3957(2) 0.52622(10) 0.0481(6) Uani 1 d . . H9A H 0.1451(19) 0.3490(18) 0.5575(7) 0.072(8) Uiso 1 d . . H9B H 0.1679(17) 0.3889(16) 0.4986(6) 0.042(6) Uiso 1 d . . C10 C 0.2060(3) 0.5939(3) 0.54237(15) 0.0739(9) Uani 1 d . . H10A H 0.2641(24) 0.5586(24) 0.5731(10) 0.124(11) Uiso 1 d . . H10B H 0.2551(21) 0.5900(21) 0.5116(8) 0.086(10) Uiso 1 d . . H10C H 0.1721(25) 0.6833(24) 0.5555(9) 0.131(11) Uiso 1 d . . C11 C 0.0091(2) 0.1671(2) 0.44094(9) 0.0484(6) Uani 1 d . . C12 C 0.0065(2) 0.2678(2) 0.39679(8) 0.0468(6) Uani 1 d . . C13 C 0.0502(3) 0.2067(3) 0.34587(11) 0.0660(8) Uani 1 d . . H13A H 0.1434(20) 0.1663(20) 0.3499(8) 0.077(8) Uiso 1 d . . H13B H -0.0090(20) 0.1335(20) 0.3366(8) 0.088(9) Uiso 1 d . . H13C H 0.0545(18) 0.2738(18) 0.3221(7) 0.063(7) Uiso 1 d . . C14 C -0.1262(2) 0.3164(2) 0.39164(9) 0.0511(6) Uani 1 d . . C15 C -0.2318(3) 0.3502(3) 0.38604(10) 0.0724(9) Uani 1 d . . H15 H -0.3157(23) 0.3816(22) 0.3836(9) 0.104(11) Uiso 1 d . . C21 C 0.2210(2) 0.1625(2) 0.79322(9) 0.0473(6) Uani 1 d . . H21 H 0.2105(16) 0.1253(14) 0.8310(6) 0.041(5) Uiso 1 d . . N21 N 0.2901(2) 0.2866(2) 0.79850(7) 0.0456(5) Uani 1 d . . O21 O 0.2299(2) -0.0401(2) 0.75640(7) 0.0907(6) Uani 1 d . . C22 C 0.0922(3) 0.2021(2) 0.76866(11) 0.0591(7) Uani 1 d . . H22A H 0.0572(17) 0.1403(16) 0.7451(7) 0.059(7) Uiso 1 d . . H22B H 0.0243(25) 0.2203(22) 0.7967(8) 0.103(10) Uiso 1 d . . O22 O 0.39899(15) 0.44053(14) 0.84047(5) 0.0602(5) Uani 1 d . . C23 C 0.1294(2) 0.3188(2) 0.73837(9) 0.0493(6) Uani 1 d . . H23 H 0.4668(29) 0.0567(30) 0.8836(11) 0.166(13) Uiso 1 d . . O23 O 0.45634(14) 0.12963(14) 0.85718(6) 0.0614(5) Uani 1 d . . C24 C 0.0681(3) 0.3779(3) 0.69733(10) 0.0621(7) Uani 1 d . . H24 H -0.0160(20) 0.3402(17) 0.6842(7) 0.062(7) Uiso 1 d . . C25 C 0.1282(3) 0.4838(3) 0.67518(11) 0.0666(8) Uani 1 d . . H25 H 0.0925(21) 0.5240(19) 0.6463(8) 0.081(9) Uiso 1 d . . C26 C 0.2416(3) 0.5295(2) 0.69387(10) 0.0609(7) Uani 1 d . . H26 H 0.2901(18) 0.6029(18) 0.6798(7) 0.056(7) Uiso 1 d . . C27 C 0.3030(2) 0.4733(2) 0.73627(9) 0.0500(6) Uani 1 d . . H27 H 0.3890(18) 0.5067(16) 0.7496(7) 0.054(6) Uiso 1 d . . C28 C 0.2448(2) 0.3665(2) 0.75741(8) 0.0444(6) Uani 1 d . . C29 C 0.2997(3) 0.0759(2) 0.75813(11) 0.0567(7) Uani 1 d . . H29A H 0.3983(18) 0.0590(16) 0.7742(6) 0.052(6) Uiso 1 d . . H29B H 0.3007(18) 0.1087(17) 0.7235(8) 0.060(7) Uiso 1 d . . C30 C 0.2779(5) -0.1262(4) 0.7189(2) 0.1041(12) Uani 1 d . . H30A H 0.2877(44) -0.0758(40) 0.6796(16) 0.286(26) Uiso 1 d . . H30B H 0.3537(22) -0.1479(23) 0.7294(10) 0.080(12) Uiso 1 d . . H30C H 0.2294(26) -0.2128(27) 0.7301(10) 0.144(13) Uiso 1 d . . C31 C 0.3616(2) 0.3298(2) 0.83886(8) 0.0465(6) Uani 1 d . . C32 C 0.3987(2) 0.2358(2) 0.88254(8) 0.0499(6) Uani 1 d . . C33 C 0.4977(3) 0.2973(3) 0.91939(12) 0.0669(8) Uani 1 d . . H33A H 0.5231(18) 0.2293(19) 0.9472(7) 0.072(7) Uiso 1 d . . H33B H 0.5801(21) 0.3224(21) 0.8987(8) 0.094(9) Uiso 1 d . . H33C H 0.4591(21) 0.3681(21) 0.9333(9) 0.092(10) Uiso 1 d . . C34 C 0.2815(2) 0.1968(2) 0.91206(9) 0.0526(6) Uani 1 d . . C35 C 0.1920(3) 0.1639(3) 0.93608(10) 0.0684(8) Uani 1 d . . H35 H 0.1238(26) 0.1242(23) 0.9530(10) 0.125(12) Uiso 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 C1 0.049(2) 0.0358(14) 0.0482(14) 0.0015(11) 0.0000(13) 0.0036(12) N1 0.0540(12) 0.0382(11) 0.0432(11) -0.0004(10) -0.0012(10) 0.0008(9) O1 0.0522(10) 0.0399(9) 0.0709(10) -0.0069(8) -0.0033(8) -0.0013(9) C2 0.050(2) 0.054(2) 0.056(2) -0.0019(13) 0.0007(15) 0.0028(14) O2 0.1010(13) 0.0436(10) 0.0588(10) -0.0077(9) -0.0021(10) 0.0077(11) C3 0.0446(15) 0.058(2) 0.052(2) 0.0058(14) -0.0005(13) -0.0057(13) O3 0.0587(11) 0.0516(11) 0.0574(11) 0.0070(10) -0.0034(9) -0.0126(10) C4 0.051(2) 0.072(2) 0.060(2) 0.006(2) 0.0079(14) -0.004(2) C5 0.072(2) 0.071(2) 0.073(2) 0.026(2) 0.001(2) -0.013(2) C6 0.082(2) 0.047(2) 0.088(2) 0.015(2) -0.013(2) -0.005(2) C7 0.069(2) 0.050(2) 0.066(2) 0.007(2) -0.009(2) -0.0053(14) C8 0.0498(14) 0.0412(14) 0.0520(15) 0.0044(13) -0.0074(13) -0.0036(13) C9 0.048(2) 0.045(2) 0.052(2) 0.0010(14) 0.000(2) 0.0002(14) C10 0.067(2) 0.062(2) 0.093(3) -0.012(2) 0.003(2) -0.015(2) C11 0.0477(14) 0.0424(15) 0.055(2) -0.0011(13) -0.0009(13) 0.0001(13) C12 0.0441(15) 0.0470(15) 0.049(2) -0.0001(12) 0.0052(13) -0.0044(13) C13 0.085(3) 0.058(2) 0.054(2) 0.001(2) 0.005(2) 0.002(2) C14 0.051(2) 0.051(2) 0.052(2) 0.0071(12) 0.0034(14) -0.0004(14) C15 0.057(2) 0.091(2) 0.069(2) 0.020(2) 0.004(2) 0.013(2) C21 0.059(2) 0.0368(14) 0.046(2) -0.0004(12) 0.0057(14) -0.0082(13) N21 0.0550(13) 0.0350(10) 0.0469(12) -0.0023(10) -0.0040(10) -0.0064(10) O21 0.0973(14) 0.0486(11) 0.126(2) -0.0336(11) 0.0249(12) -0.0157(11) C22 0.055(2) 0.058(2) 0.064(2) -0.010(2) 0.003(2) -0.0112(15) O22 0.0808(12) 0.0399(9) 0.0598(10) -0.0002(8) -0.0060(9) -0.0153(10) C23 0.054(2) 0.0437(15) 0.050(2) -0.0064(13) 0.0007(13) 0.0021(13) O23 0.0760(12) 0.0481(10) 0.0601(11) 0.0039(9) 0.0104(9) 0.0160(9) C24 0.063(2) 0.062(2) 0.062(2) -0.012(2) -0.004(2) 0.008(2) C25 0.084(2) 0.060(2) 0.056(2) 0.001(2) 0.002(2) 0.020(2) C26 0.078(2) 0.044(2) 0.060(2) 0.0022(15) 0.013(2) 0.002(2) C27 0.061(2) 0.042(2) 0.047(2) -0.0039(13) 0.0045(14) -0.0003(15) C28 0.050(2) 0.0381(14) 0.0456(15) -0.0029(13) 0.0056(12) 0.0010(12) C29 0.068(2) 0.045(2) 0.057(2) -0.0049(14) 0.007(2) -0.0028(14) C30 0.127(4) 0.056(2) 0.129(4) -0.035(2) 0.003(3) 0.009(3) C31 0.0455(15) 0.0447(15) 0.049(2) -0.0030(13) 0.0080(12) 0.0026(12) C32 0.054(2) 0.0449(15) 0.051(2) 0.0012(12) -0.0003(14) 0.0055(13) C33 0.072(2) 0.066(2) 0.062(2) 0.008(2) -0.011(2) 0.001(2) C34 0.063(2) 0.0417(15) 0.053(2) 0.0021(13) 0.0054(14) 0.0029(14) C35 0.075(2) 0.065(2) 0.065(2) 0.002(2) 0.015(2) -0.003(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 C1 N1 1.500(2) . ? C1 C9 1.512(3) . ? C1 C2 1.534(3) . ? N1 C11 1.351(2) . ? N1 C8 1.434(2) . ? O1 C9 1.412(2) . ? O1 C10 1.435(3) . ? C2 C3 1.503(3) . ? O2 C11 1.226(2) . ? C3 C8 1.378(3) . ? C3 C4 1.388(3) . ? O3 C12 1.426(2) . ? C4 C5 1.368(3) . ? C5 C6 1.369(3) . ? C6 C7 1.398(3) . ? C7 C8 1.388(3) . ? C11 C12 1.557(3) . ? C12 C14 1.466(3) . ? C12 C13 1.531(3) . ? C14 C15 1.154(3) . ? C21 N21 1.495(2) . ? C21 C29 1.520(3) . ? C21 C22 1.528(3) . ? N21 C31 1.354(2) . ? N21 C28 1.432(2) . ? O21 C30 1.415(3) . ? O21 C29 1.418(3) . ? C22 C23 1.507(3) . ? O22 C31 1.230(2) . ? C23 C28 1.380(3) . ? C23 C24 1.381(3) . ? O23 C32 1.425(2) . ? C24 C25 1.398(3) . ? C25 C26 1.352(3) . ? C26 C27 1.395(3) . ? C27 C28 1.387(3) . ? C31 C32 1.548(3) . ? C32 C34 1.485(3) . ? C32 C33 1.538(3) . ? C34 C35 1.164(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 N1 C1 C9 109.2(2) . . ? N1 C1 C2 102.6(2) . . ? C9 C1 C2 112.1(2) . . ? C11 N1 C8 123.2(2) . . ? C11 N1 C1 128.3(2) . . ? C8 N1 C1 107.3(2) . . ? C9 O1 C10 111.5(2) . . ? C3 C2 C1 102.9(2) . . ? C8 C3 C4 119.7(2) . . ? C8 C3 C2 109.9(2) . . ? C4 C3 C2 130.4(2) . . ? C5 C4 C3 119.4(3) . . ? C4 C5 C6 120.1(3) . . ? C5 C6 C7 122.6(3) . . ? C8 C7 C6 115.9(3) . . ? C3 C8 C7 122.3(2) . . ? C3 C8 N1 109.5(2) . . ? C7 C8 N1 128.2(2) . . ? O1 C9 C1 107.3(2) . . ? O2 C11 N1 121.3(2) . . ? O2 C11 C12 119.6(2) . . ? N1 C11 C12 119.1(2) . . ? O3 C12 C14 112.3(2) . . ? O3 C12 C13 109.7(2) . . ? C14 C12 C13 110.1(2) . . ? O3 C12 C11 106.3(2) . . ? C14 C12 C11 108.7(2) . . ? C13 C12 C11 109.7(2) . . ? C15 C14 C12 176.8(3) . . ? N21 C21 C29 109.0(2) . . ? N21 C21 C22 102.3(2) . . ? C29 C21 C22 112.3(2) . . ? C31 N21 C28 123.4(2) . . ? C31 N21 C21 128.5(2) . . ? C28 N21 C21 106.9(2) . . ? C30 O21 C29 113.4(2) . . ? C23 C22 C21 102.6(2) . . ? C28 C23 C24 120.2(2) . . ? C28 C23 C22 109.3(2) . . ? C24 C23 C22 130.5(3) . . ? C23 C24 C25 118.1(3) . . ? C26 C25 C24 121.4(3) . . ? C25 C26 C27 121.3(3) . . ? C28 C27 C26 117.2(2) . . ? C23 C28 C27 121.8(2) . . ? C23 C28 N21 109.3(2) . . ? C27 C28 N21 128.8(2) . . ? O21 C29 C21 105.4(2) . . ? O22 C31 N21 121.0(2) . . ? O22 C31 C32 120.3(2) . . ? N21 C31 C32 118.7(2) . . ? O23 C32 C34 110.9(2) . . ? O23 C32 C33 109.8(2) . . ? C34 C32 C33 109.8(2) . . ? O23 C32 C31 105.7(2) . . ? C34 C32 C31 110.5(2) . . ? C33 C32 C31 110.2(2) . . ? C35 C34 C32 178.0(3) . . ? _refine_diff_density_max 0.097 _refine_diff_density_min -0.094 _refine_diff_density_rms 0.023 #====END