Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_name 'Steven V. Ley' _publ_contact_author_address ; Chemistry University of Cambridge Lensfield Road Cambridge CB2 1EW UNITED KINGDOM ; _publ_contact_author_email SVL1000@CAM.AC.UK _publ_section_title ; An efficient, asymmetric organocatalyst-mediated conjugate addition of nitroalkanes to unsaturated cyclic and acyclic systems ; loop_ _publ_author_name 'S. Ley' 'Stacey Brenner' 'Jorge G. Fortanet' 'Claire E.T Mitchell' # Attachment 'SL0519.CIF' data_sl0519 _database_code_depnum_ccdc_archive 'CCDC 287832' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C12 H15 N O3' _chemical_formula_sum 'C12 H15 N O3' _chemical_formula_weight 221.25 _chemical_absolute_configuration 'not determined' 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 P2(1)2(1)2(1) _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 5.6440(1) _cell_length_b 8.4770(2) _cell_length_c 25.1210(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1201.89(4) _cell_formula_units_Z 4 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 13723 _cell_measurement_theta_min 1.00 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.46 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.23 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.223 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 472 _exptl_absorpt_coefficient_mu 0.088 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.915 _exptl_absorpt_correction_T_max 0.981 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; 1061 Friedel pairs were averaged for the refinement. The absolute structure was assigned from the known configuration of the starting material. This experiment determined RELATIVE stereochemistry. ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_measurement_device_type 'Nonius Kappa CCD' _diffrn_measurement_method 'Thin slice \w and \f scans' _diffrn_reflns_number 9256 _diffrn_reflns_av_R_equivalents 0.0273 _diffrn_reflns_av_sigmaI/netI 0.0211 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -32 _diffrn_reflns_limit_l_max 32 _diffrn_reflns_theta_min 3.70 _diffrn_reflns_theta_max 27.44 _reflns_number_total 1600 _reflns_number_gt 1518 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Nonius B.V. 1998)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction ; HKL Denzo and Scalepack (Otwinowski & Minor 1997) ; _computing_structure_solution 'SIR-92 (Altomare et al. 1994)' _computing_structure_refinement 'SHELXL-97 (Sheldrick 1997)' _computing_publication_material 'SHELXL-97 (Sheldrick 1997)' _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^)+(0.0322P)^2^+0.2195P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.1(13) _refine_ls_number_reflns 1600 _refine_ls_number_parameters 147 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0341 _refine_ls_R_factor_gt 0.0312 _refine_ls_wR_factor_ref 0.0770 _refine_ls_wR_factor_gt 0.0752 _refine_ls_goodness_of_fit_ref 1.074 _refine_ls_restrained_S_all 1.074 _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 N1 N 0.7733(2) 0.57859(16) 0.18424(5) 0.0311(3) Uani 1 1 d . . . O1 O 0.1886(2) 0.13733(14) 0.13838(5) 0.0423(3) Uani 1 1 d . . . O2 O 0.9019(2) 0.66210(14) 0.15753(5) 0.0464(3) Uani 1 1 d . . . O3 O 0.6150(2) 0.63007(15) 0.21257(5) 0.0482(3) Uani 1 1 d . . . C1 C 0.4027(4) -0.09565(19) 0.11872(7) 0.0433(4) Uani 1 1 d . . . H1A H 0.2467 -0.1465 0.1184 0.065 Uiso 1 1 calc R . . H1B H 0.5088 -0.1539 0.1425 0.065 Uiso 1 1 calc R . . H1C H 0.4686 -0.0955 0.0826 0.065 Uiso 1 1 calc R . . C2 C 0.3780(3) 0.07069(18) 0.13802(6) 0.0298(3) Uani 1 1 d . . . C3 C 0.6011(3) 0.14863(18) 0.15813(6) 0.0295(3) Uani 1 1 d . . . H3A H 0.7366 0.1135 0.1361 0.035 Uiso 1 1 calc R . . H3B H 0.6308 0.1138 0.1952 0.035 Uiso 1 1 calc R . . C4 C 0.5880(3) 0.32979(17) 0.15685(5) 0.0258(3) Uani 1 1 d . . . H4 H 0.4468 0.3633 0.1781 0.031 Uiso 1 1 calc R . . C5 C 0.8096(3) 0.40154(17) 0.18272(6) 0.0287(3) Uani 1 1 d . . . H5 H 0.9501 0.3776 0.1598 0.034 Uiso 1 1 calc R . . C6 C 0.8610(3) 0.3467(2) 0.23908(6) 0.0449(4) Uani 1 1 d . . . H6A H 0.9831 0.4142 0.2549 0.067 Uiso 1 1 calc R . . H6B H 0.9172 0.2373 0.2383 0.067 Uiso 1 1 calc R . . H6C H 0.7160 0.3530 0.2604 0.067 Uiso 1 1 calc R . . C7 C 0.5573(2) 0.39103(16) 0.10022(5) 0.0254(3) Uani 1 1 d . . . C8 C 0.7161(3) 0.3473(2) 0.06035(6) 0.0341(3) Uani 1 1 d . . . H8 H 0.8450 0.2795 0.0686 0.041 Uiso 1 1 calc R . . C9 C 0.6875(3) 0.4019(2) 0.00879(6) 0.0432(4) Uani 1 1 d . . . H9 H 0.7959 0.3704 -0.0181 0.052 Uiso 1 1 calc R . . C10 C 0.5029(3) 0.5014(2) -0.00368(6) 0.0439(4) Uani 1 1 d . . . H10 H 0.4839 0.5383 -0.0391 0.053 Uiso 1 1 calc R . . C11 C 0.3453(3) 0.5476(2) 0.03546(7) 0.0395(4) Uani 1 1 d . . . H11 H 0.2185 0.6170 0.0270 0.047 Uiso 1 1 calc R . . C12 C 0.3729(3) 0.49209(18) 0.08740(6) 0.0315(3) Uani 1 1 d . . . H12 H 0.2643 0.5239 0.1142 0.038 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 N1 0.0303(6) 0.0328(7) 0.0303(6) -0.0051(5) -0.0021(5) -0.0003(6) O1 0.0252(5) 0.0386(7) 0.0631(7) -0.0010(6) 0.0011(5) 0.0005(5) O2 0.0451(7) 0.0350(6) 0.0593(7) 0.0009(6) 0.0093(6) -0.0077(6) O3 0.0531(8) 0.0440(7) 0.0474(6) -0.0098(6) 0.0135(6) 0.0111(7) C1 0.0460(9) 0.0304(8) 0.0534(9) -0.0006(7) -0.0095(8) 0.0002(8) C2 0.0298(7) 0.0286(7) 0.0311(6) 0.0045(6) 0.0022(6) -0.0006(7) C3 0.0255(7) 0.0290(7) 0.0339(7) 0.0032(6) -0.0011(6) 0.0010(6) C4 0.0223(6) 0.0281(7) 0.0271(6) 0.0002(5) 0.0016(6) 0.0007(6) C5 0.0278(7) 0.0283(7) 0.0300(7) -0.0025(6) -0.0014(6) 0.0019(7) C6 0.0511(10) 0.0445(9) 0.0390(8) 0.0041(7) -0.0168(8) -0.0033(9) C7 0.0244(6) 0.0249(6) 0.0267(6) -0.0017(5) -0.0005(5) -0.0032(6) C8 0.0320(8) 0.0392(8) 0.0310(7) -0.0018(6) 0.0028(6) 0.0038(8) C9 0.0466(9) 0.0537(10) 0.0293(7) -0.0028(7) 0.0063(7) -0.0016(10) C10 0.0533(10) 0.0480(10) 0.0304(7) 0.0067(7) -0.0056(8) -0.0094(9) C11 0.0385(9) 0.0361(8) 0.0439(8) 0.0080(7) -0.0084(8) 0.0004(7) C12 0.0289(7) 0.0303(7) 0.0352(7) 0.0011(6) 0.0009(6) 0.0019(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 N1 O2 1.2158(17) . ? N1 O3 1.2227(17) . ? N1 C5 1.5152(19) . ? O1 C2 1.2092(19) . ? C1 C2 1.498(2) . ? C1 H1A 0.9800 . ? C1 H1B 0.9800 . ? C1 H1C 0.9800 . ? C2 C3 1.509(2) . ? C3 C4 1.538(2) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 C7 1.5242(19) . ? C4 C5 1.535(2) . ? C4 H4 1.0000 . ? C5 C6 1.518(2) . ? C5 H5 1.0000 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 C12 1.386(2) . ? C7 C8 1.394(2) . ? C8 C9 1.385(2) . ? C8 H8 0.9500 . ? C9 C10 1.377(3) . ? C9 H9 0.9500 . ? C10 C11 1.383(2) . ? C10 H10 0.9500 . ? C11 C12 1.396(2) . ? C11 H11 0.9500 . ? C12 H12 0.9500 . ? 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 O2 N1 O3 123.34(14) . . ? O2 N1 C5 118.82(13) . . ? O3 N1 C5 117.84(13) . . ? C2 C1 H1A 109.5 . . ? C2 C1 H1B 109.5 . . ? H1A C1 H1B 109.5 . . ? C2 C1 H1C 109.5 . . ? H1A C1 H1C 109.5 . . ? H1B C1 H1C 109.5 . . ? O1 C2 C1 121.64(15) . . ? O1 C2 C3 122.05(13) . . ? C1 C2 C3 116.29(14) . . ? C2 C3 C4 112.94(13) . . ? C2 C3 H3A 109.0 . . ? C4 C3 H3A 109.0 . . ? C2 C3 H3B 109.0 . . ? C4 C3 H3B 109.0 . . ? H3A C3 H3B 107.8 . . ? C7 C4 C5 110.65(12) . . ? C7 C4 C3 111.43(12) . . ? C5 C4 C3 110.33(12) . . ? C7 C4 H4 108.1 . . ? C5 C4 H4 108.1 . . ? C3 C4 H4 108.1 . . ? N1 C5 C6 107.80(12) . . ? N1 C5 C4 107.05(12) . . ? C6 C5 C4 115.41(13) . . ? N1 C5 H5 108.8 . . ? C6 C5 H5 108.8 . . ? C4 C5 H5 108.8 . . ? C5 C6 H6A 109.5 . . ? C5 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C5 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C12 C7 C8 118.70(13) . . ? C12 C7 C4 120.85(12) . . ? C8 C7 C4 120.45(13) . . ? C9 C8 C7 120.53(15) . . ? C9 C8 H8 119.7 . . ? C7 C8 H8 119.7 . . ? C10 C9 C8 120.38(16) . . ? C10 C9 H9 119.8 . . ? C8 C9 H9 119.8 . . ? C9 C10 C11 119.93(15) . . ? C9 C10 H10 120.0 . . ? C11 C10 H10 120.0 . . ? C10 C11 C12 119.82(16) . . ? C10 C11 H11 120.1 . . ? C12 C11 H11 120.1 . . ? C7 C12 C11 120.64(14) . . ? C7 C12 H12 119.7 . . ? C11 C12 H12 119.7 . . ? 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 O1 C2 C3 C4 -23.5(2) . . . . ? C1 C2 C3 C4 157.95(13) . . . . ? C2 C3 C4 C7 -62.14(16) . . . . ? C2 C3 C4 C5 174.53(11) . . . . ? O2 N1 C5 C6 121.16(15) . . . . ? O3 N1 C5 C6 -58.78(18) . . . . ? O2 N1 C5 C4 -114.10(15) . . . . ? O3 N1 C5 C4 65.96(16) . . . . ? C7 C4 C5 N1 61.09(14) . . . . ? C3 C4 C5 N1 -175.13(12) . . . . ? C7 C4 C5 C6 -178.93(13) . . . . ? C3 C4 C5 C6 -55.15(17) . . . . ? C5 C4 C7 C12 -110.74(15) . . . . ? C3 C4 C7 C12 126.12(14) . . . . ? C5 C4 C7 C8 68.70(17) . . . . ? C3 C4 C7 C8 -54.44(19) . . . . ? C12 C7 C8 C9 -1.0(2) . . . . ? C4 C7 C8 C9 179.51(15) . . . . ? C7 C8 C9 C10 0.6(3) . . . . ? C8 C9 C10 C11 0.1(3) . . . . ? C9 C10 C11 C12 -0.5(3) . . . . ? C8 C7 C12 C11 0.7(2) . . . . ? C4 C7 C12 C11 -179.88(14) . . . . ? C10 C11 C12 C7 0.1(2) . . . . ? _diffrn_measured_fraction_theta_max 0.982 _diffrn_reflns_theta_full 27.44 _diffrn_measured_fraction_theta_full 0.982 _refine_diff_density_max 0.144 _refine_diff_density_min -0.125 _refine_diff_density_rms 0.028