# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2006 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _publ_contact_author_name 'Donald Craig' _publ_contact_author_address ; Department of Chemistry Imperial College London South Kensington Campus London SW7 2AZ UNITED KINGDOM ; _publ_section_title ; Silyl-modified Bellus-Claisen Rearrangement ; loop_ _publ_author_name D.Craig N.P.King D.M.Mountford _publ_contact_author_email D.CRAIG@IMPERIAL.AC.UK # Attachment 'DC0404.cif' data_DC0404 _database_code_depnum_ccdc_archive 'CCDC 623206' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C18 H25 N O2' _chemical_formula_weight 287.39 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 '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) 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 6.122(3) _cell_length_b 15.768(2) _cell_length_c 17.431(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1682.7(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 10.57 _cell_measurement_theta_max 22.26 _exptl_crystal_description needles _exptl_crystal_colour Colourless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.134 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 0.574 _exptl_absorpt_correction_type Empirical _exptl_absorpt_correction_T_min 0.3857 _exptl_absorpt_correction_T_max 0.7881 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 1.54178 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker P4' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count 97 _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1682 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0523 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.78 _diffrn_reflns_theta_max 64.99 _reflns_number_total 1682 _reflns_number_gt 1192 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker XSCANS' _computing_cell_refinement 'Bruker XSCANS' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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. Results of chirality/polarity tests #_refine_ls_R_factor_obs+ 0.0552 #_refine_ls_wR_factor_obs+ 0.1474 #_refine_ls_abs_structure_Flack+ 0.4(9) #_refine_ls_R_factor_obs- 0.0552 #_refine_ls_wR_factor_obs- 0.1473 #_refine_ls_abs_structure_Flack- 0.6(9) ; _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^)+(0.0768P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0048(8) _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 0.3(8) _refine_ls_number_reflns 1682 _refine_ls_number_parameters 179 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0816 _refine_ls_R_factor_gt 0.0552 _refine_ls_wR_factor_ref 0.1679 _refine_ls_wR_factor_gt 0.1474 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _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 0.2922(6) 0.7029(3) 0.44638(19) 0.0850(10) Uani 1 1 d . . . C2 C 0.0980(9) 0.6901(3) 0.4036(3) 0.0812(13) Uani 1 1 d . . . H2A H -0.0143 0.6677 0.4372 0.097 Uiso 1 1 calc R . . H2B H 0.1253 0.6485 0.3638 0.097 Uiso 1 1 calc R . . C3 C 0.0173(8) 0.7710(3) 0.3673(3) 0.0754(12) Uani 1 1 d . . . H3A H -0.1100 0.7591 0.3359 0.090 Uiso 1 1 calc R . . H3B H -0.0251 0.8109 0.4070 0.090 Uiso 1 1 calc R . . N4 N 0.1894(6) 0.8082(2) 0.3198(2) 0.0662(8) Uani 1 1 d . . . C5 C 0.4000(8) 0.8152(3) 0.3593(3) 0.0759(12) Uani 1 1 d . . . H5A H 0.3914 0.8593 0.3980 0.091 Uiso 1 1 calc R . . H5B H 0.5123 0.8311 0.3228 0.091 Uiso 1 1 calc R . . C6 C 0.4606(8) 0.7323(4) 0.3969(3) 0.0815(13) Uani 1 1 d . . . H6A H 0.4880 0.6901 0.3576 0.098 Uiso 1 1 calc R . . H6B H 0.5941 0.7397 0.4261 0.098 Uiso 1 1 calc R . . C7 C 0.1261(7) 0.8588(3) 0.2604(2) 0.0651(10) Uani 1 1 d . . . O7 O -0.0690(5) 0.8645(2) 0.2422(2) 0.0805(9) Uani 1 1 d . . . C8 C 0.2981(8) 0.9077(3) 0.2159(2) 0.0665(10) Uani 1 1 d . . . H8A H 0.4384 0.8788 0.2228 0.080 Uiso 1 1 calc R . . C9 C 0.3162(4) 0.99611(15) 0.25219(17) 0.0627(9) Uani 1 1 d G . . C10 C 0.1353(4) 1.04936(19) 0.25316(18) 0.0755(11) Uani 1 1 d G . . H10A H 0.0038 1.0313 0.2320 0.091 Uiso 1 1 calc R . . C11 C 0.1509(5) 1.12960(18) 0.2857(2) 0.0829(13) Uani 1 1 d G . . H11A H 0.0298 1.1652 0.2864 0.099 Uiso 1 1 calc R . . C12 C 0.3474(6) 1.15658(17) 0.3173(2) 0.0956(16) Uani 1 1 d G . . H12A H 0.3578 1.2103 0.3391 0.115 Uiso 1 1 calc R . . C13 C 0.5283(5) 1.1033(2) 0.3164(2) 0.0987(17) Uani 1 1 d G . . H13A H 0.6598 1.1214 0.3375 0.118 Uiso 1 1 calc R . . C14 C 0.5127(4) 1.02310(19) 0.2838(2) 0.0822(13) Uani 1 1 d G . . H14A H 0.6337 0.9875 0.2832 0.099 Uiso 1 1 calc R . . C15 C 0.2493(10) 0.9113(3) 0.1297(2) 0.0778(13) Uani 1 1 d . . . H15A H 0.1114 0.9417 0.1219 0.093 Uiso 1 1 calc R . . C16 C 0.2269(13) 0.8237(4) 0.0976(3) 0.0939(17) Uani 1 1 d . . . H16A H 0.3503 0.7895 0.1008 0.113 Uiso 1 1 calc R . . C17 C 0.0591(17) 0.7900(5) 0.0663(4) 0.134(3) Uani 1 1 d . . . H17A H -0.0694 0.8210 0.0615 0.160 Uiso 1 1 calc R . . H17B H 0.0654 0.7345 0.0485 0.160 Uiso 1 1 calc R . . C18 C 0.4297(14) 0.9579(4) 0.0870(3) 0.107(2) Uani 1 1 d . . . H18A H 0.4526 1.0124 0.1115 0.128 Uiso 1 1 calc R . . H18B H 0.5639 0.9257 0.0920 0.128 Uiso 1 1 calc R . . C19 C 0.3859(19) 0.9727(5) 0.0024(3) 0.136(3) Uani 1 1 d . . . H19A H 0.3430 0.9196 -0.0213 0.163 Uiso 1 1 calc R . . H19B H 0.2657 1.0123 -0.0031 0.163 Uiso 1 1 calc R . . C20 C 0.581(2) 1.0068(5) -0.0379(4) 0.167(5) Uani 1 1 d . . . H20A H 0.5460 1.0161 -0.0910 0.250 Uiso 1 1 calc R . . H20B H 0.6986 0.9669 -0.0341 0.250 Uiso 1 1 calc R . . H20C H 0.6234 1.0595 -0.0148 0.250 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 0.077(2) 0.107(3) 0.0706(17) 0.0239(18) -0.0029(16) -0.008(2) C2 0.077(3) 0.085(3) 0.081(3) 0.023(3) -0.009(3) -0.008(3) C3 0.059(2) 0.090(3) 0.077(3) 0.012(2) 0.005(2) -0.004(2) N4 0.0567(17) 0.077(2) 0.0650(17) 0.0091(17) -0.0021(16) 0.0001(16) C5 0.062(2) 0.097(3) 0.068(2) 0.013(2) -0.006(2) -0.010(2) C6 0.069(3) 0.108(3) 0.067(2) 0.022(2) 0.000(2) 0.004(3) C7 0.062(2) 0.071(2) 0.062(2) 0.0074(18) -0.0011(19) 0.007(2) O7 0.0668(18) 0.089(2) 0.086(2) 0.0099(17) -0.0110(17) 0.0078(16) C8 0.067(2) 0.070(2) 0.062(2) 0.0043(19) 0.002(2) 0.007(2) C9 0.063(2) 0.069(2) 0.0556(18) 0.0062(18) 0.003(2) -0.0030(19) C10 0.074(2) 0.077(2) 0.076(2) 0.003(2) 0.000(3) 0.006(2) C11 0.083(3) 0.078(3) 0.087(3) -0.001(2) 0.009(3) 0.007(3) C12 0.103(4) 0.087(3) 0.097(3) -0.011(3) 0.008(4) -0.016(3) C13 0.085(3) 0.101(4) 0.111(4) -0.007(3) -0.015(3) -0.017(3) C14 0.073(3) 0.082(3) 0.092(3) 0.008(2) -0.011(3) -0.003(2) C15 0.105(4) 0.069(2) 0.059(2) 0.002(2) -0.002(2) 0.008(3) C16 0.127(5) 0.082(3) 0.072(2) -0.003(3) -0.001(3) 0.002(3) C17 0.161(8) 0.123(6) 0.117(5) -0.031(4) 0.001(5) -0.027(6) C18 0.155(6) 0.091(3) 0.074(3) 0.007(3) 0.020(4) -0.006(4) C19 0.224(11) 0.116(5) 0.068(3) 0.009(3) 0.016(5) -0.007(6) C20 0.287(15) 0.122(6) 0.091(4) 0.004(4) 0.048(7) -0.052(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 O1 C2 1.418(6) . ? O1 C6 1.422(6) . ? C2 C3 1.507(7) . ? C3 N4 1.463(6) . ? N4 C7 1.363(5) . ? N4 C5 1.467(6) . ? C5 C6 1.509(7) . ? C7 O7 1.239(5) . ? C7 C8 1.519(6) . ? C8 C15 1.533(6) . ? C8 C9 1.535(5) . ? C9 C10 1.3900 . ? C9 C14 1.3900 . ? C10 C11 1.3900 . ? C11 C12 1.3900 . ? C12 C13 1.3900 . ? C13 C14 1.3900 . ? C15 C16 1.497(7) . ? C15 C18 1.521(9) . ? C16 C17 1.278(11) . ? C18 C19 1.517(8) . ? C19 C20 1.485(14) . ? 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 C6 109.6(3) . . ? O1 C2 C3 112.0(4) . . ? N4 C3 C2 109.9(4) . . ? C7 N4 C3 117.4(4) . . ? C7 N4 C5 124.2(4) . . ? C3 N4 C5 113.4(3) . . ? N4 C5 C6 110.8(4) . . ? O1 C6 C5 111.5(4) . . ? O7 C7 N4 120.7(4) . . ? O7 C7 C8 120.1(4) . . ? N4 C7 C8 119.3(4) . . ? C7 C8 C15 112.6(4) . . ? C7 C8 C9 107.5(3) . . ? C15 C8 C9 112.7(3) . . ? C10 C9 C14 120.0 . . ? C10 C9 C8 119.7(3) . . ? C14 C9 C8 120.3(2) . . ? C11 C10 C9 120.0 . . ? C10 C11 C12 120.0 . . ? C11 C12 C13 120.0 . . ? C14 C13 C12 120.0 . . ? C13 C14 C9 120.0 . . ? C16 C15 C18 109.3(5) . . ? C16 C15 C8 110.5(4) . . ? C18 C15 C8 110.8(5) . . ? C17 C16 C15 128.0(7) . . ? C19 C18 C15 114.9(7) . . ? C20 C19 C18 112.0(9) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 64.99 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.119 _refine_diff_density_min -0.150 _refine_diff_density_rms 0.034 #===END