Supplementary Material (ESI) for Chemical Communications This journal is (C) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Kumaraswamy Gullapalli' _publ_contact_author_email 'GKSWAMY IICT@YAHOO.CO.IN' _publ_section_title ; Highly enantioselctive concise route for the syntheses of seven-membered oxacycles and six-membered carbocycles by Cu-catalyzed asymmetric [2, 3]-sigmatropic rearrangement ; loop_ _publ_author_name 'Kumaraswamy Gullapalli' 'Sridhar Balasubramanian' 'Jagadeesh Bharatam' 'Ramakrishna Duggirala Subrahmanya' ; S.Kadivendi ; 'Naresh Police' data_ac92 _database_code_depnum_ccdc_archive 'CCDC 690682' _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C19 H18 O3' _chemical_formula_sum 'C19 H18 O3' _chemical_formula_weight 294.33 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' O O 0.0106 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 'P 21 21 21' _symmetry_int_tables_number 19 _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, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' _cell_length_a 10.1848(8) _cell_length_b 17.5488(14) _cell_length_c 8.8167(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1575.8(2) _cell_formula_units_Z 4 _cell_measurement_temperature 294(2) _cell_measurement_reflns_used 8828 _cell_measurement_theta_min 2.31 _cell_measurement_theta_max 27.13 _chemical_absolute_configuration unk _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.23 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.241 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 624 _exptl_absorpt_coefficient_mu 0.083 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 294(2) _diffrn_radiation_probe x-ray _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD Area Detector' _diffrn_measurement_device 'Bruker SMART APEX CCD area-detector' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15193 _diffrn_reflns_av_R_equivalents 0.0185 _diffrn_reflns_av_sigmaI/netI 0.0106 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 25.00 _reflns_number_total 1616 _reflns_number_gt 1541 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'SMART (Bruker, 2001)' _computing_cell_refinement 'SAINT (Bruker, 2001)' _computing_data_reduction SAINT _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL/PC (Sheldrick, 1990)' _computing_publication_material SHELXL97 _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^)+(0.0592P)^2^+0.1326P] 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_number_reflns 1616 _refine_ls_number_parameters 199 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0343 _refine_ls_R_factor_gt 0.0329 _refine_ls_wR_factor_ref 0.0932 _refine_ls_wR_factor_gt 0.0913 _refine_ls_goodness_of_fit_ref 1.042 _refine_ls_restrained_S_all 1.042 _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 C1 C 0.70545(17) 0.94157(10) 0.3560(2) 0.0505(4) Uani 1 1 d . . . H1 H 0.7330 0.9692 0.2647 0.061 Uiso 1 1 calc R . . C2 C 0.69518(17) 0.85573(10) 0.3175(2) 0.0522(4) Uani 1 1 d . . . H2 H 0.6479 0.8294 0.3988 0.063 Uiso 1 1 calc R . . C3 C 0.8770(2) 0.80364(11) 0.4473(3) 0.0668(6) Uani 1 1 d . . . C4 C 1.0122(2) 0.82806(12) 0.4729(3) 0.0689(5) Uani 1 1 d . . . H4 H 1.0591 0.8015 0.5543 0.083 Uiso 1 1 calc R . . C5 C 1.0962(2) 0.85994(14) 0.3495(3) 0.0806(7) Uani 1 1 d . . . H5A H 1.1900 0.8508 0.3554 0.097 Uiso 1 1 calc R . . H5B H 1.0606 0.8601 0.2475 0.097 Uiso 1 1 calc R . . C6 C 1.03777(19) 0.91353(12) 0.4613(3) 0.0688(5) Uani 1 1 d . . . H6 H 1.1000 0.9332 0.5364 0.083 Uiso 1 1 calc R . . C7 C 0.93257(18) 0.96923(11) 0.4156(3) 0.0716(6) Uani 1 1 d . . . H7A H 0.9573 1.0194 0.4517 0.086 Uiso 1 1 calc R . . H7B H 0.9293 0.9714 0.3058 0.086 Uiso 1 1 calc R . . C8 C 0.57682(18) 0.97430(11) 0.4100(2) 0.0553(4) Uani 1 1 d . . . C9 C 0.5297(2) 1.04098(13) 0.3471(3) 0.0750(6) Uani 1 1 d . . . H9 H 0.5772 1.0653 0.2711 0.090 Uiso 1 1 calc R . . C10 C 0.4121(3) 1.07183(16) 0.3966(4) 0.0984(9) Uani 1 1 d . . . H10 H 0.3810 1.1168 0.3538 0.118 Uiso 1 1 calc R . . C11 C 0.3411(2) 1.03629(19) 0.5088(4) 0.0984(9) Uani 1 1 d . . . H11 H 0.2612 1.0566 0.5401 0.118 Uiso 1 1 calc R . . C12 C 0.3876(2) 0.97151(19) 0.5741(3) 0.0904(8) Uani 1 1 d . . . H12 H 0.3407 0.9480 0.6515 0.109 Uiso 1 1 calc R . . C13 C 0.5056(2) 0.94059(14) 0.5245(3) 0.0721(6) Uani 1 1 d . . . H13 H 0.5370 0.8963 0.5695 0.087 Uiso 1 1 calc R . . C14 C 0.62886(18) 0.84005(10) 0.1684(2) 0.0543(4) Uani 1 1 d . . . C15 C 0.6977(2) 0.84353(12) 0.0337(2) 0.0670(5) Uani 1 1 d . . . H15 H 0.7863 0.8563 0.0350 0.080 Uiso 1 1 calc R . . C16 C 0.6364(3) 0.82827(15) -0.1034(3) 0.0870(7) Uani 1 1 d . . . H16 H 0.6842 0.8295 -0.1932 0.104 Uiso 1 1 calc R . . C17 C 0.5050(3) 0.81131(14) -0.1059(4) 0.0931(9) Uani 1 1 d . . . H17 H 0.4634 0.8015 -0.1977 0.112 Uiso 1 1 calc R . . C18 C 0.4347(3) 0.80878(13) 0.0273(4) 0.0910(8) Uani 1 1 d . . . H18 H 0.3453 0.7978 0.0250 0.109 Uiso 1 1 calc R . . C19 C 0.4962(2) 0.82249(12) 0.1647(3) 0.0721(6) Uani 1 1 d . . . H19 H 0.4485 0.8199 0.2545 0.087 Uiso 1 1 calc R . . O1 O 0.80301(12) 0.95202(7) 0.47124(15) 0.0577(3) Uani 1 1 d . . . O2 O 0.82861(12) 0.82891(7) 0.31243(15) 0.0579(3) Uani 1 1 d . . . O3 O 0.81361(18) 0.76610(11) 0.5338(3) 0.1099(8) Uani 1 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 0.0489(9) 0.0513(9) 0.0511(9) 0.0021(7) 0.0010(8) 0.0010(8) C2 0.0493(9) 0.0508(9) 0.0565(9) 0.0042(8) 0.0024(8) 0.0020(8) C3 0.0643(11) 0.0529(9) 0.0832(14) 0.0182(10) -0.0105(11) 0.0032(9) C4 0.0566(10) 0.0664(11) 0.0837(14) 0.0157(11) -0.0102(11) 0.0076(9) C5 0.0537(11) 0.0856(14) 0.1026(17) 0.0125(14) 0.0122(12) 0.0157(11) C6 0.0449(9) 0.0686(11) 0.0930(15) 0.0045(12) -0.0024(11) -0.0031(9) C7 0.0477(10) 0.0552(10) 0.1119(17) 0.0079(12) 0.0057(12) -0.0050(8) C8 0.0485(9) 0.0600(10) 0.0573(10) -0.0118(9) -0.0088(9) 0.0035(8) C9 0.0689(13) 0.0709(12) 0.0853(14) -0.0053(11) -0.0115(12) 0.0142(11) C10 0.0745(15) 0.0907(17) 0.130(2) -0.0155(17) -0.0216(18) 0.0327(15) C11 0.0534(12) 0.121(2) 0.121(2) -0.051(2) -0.0097(15) 0.0211(14) C12 0.0572(12) 0.126(2) 0.0880(16) -0.0260(17) 0.0093(12) -0.0006(14) C13 0.0556(11) 0.0899(15) 0.0708(12) -0.0049(12) 0.0043(11) 0.0071(11) C14 0.0573(10) 0.0432(8) 0.0625(11) -0.0013(8) -0.0033(9) 0.0038(8) C15 0.0692(11) 0.0680(11) 0.0637(11) -0.0038(10) -0.0026(11) 0.0086(10) C16 0.114(2) 0.0831(15) 0.0641(13) -0.0114(12) -0.0082(14) 0.0195(16) C17 0.121(2) 0.0703(14) 0.0886(17) -0.0190(13) -0.0398(18) 0.0011(15) C18 0.0831(16) 0.0702(13) 0.120(2) -0.0030(15) -0.0362(18) -0.0164(12) C19 0.0641(12) 0.0670(12) 0.0853(14) 0.0024(11) -0.0087(12) -0.0107(10) O1 0.0447(6) 0.0613(7) 0.0670(7) -0.0047(6) -0.0010(6) -0.0025(5) O2 0.0544(7) 0.0547(7) 0.0646(7) 0.0014(6) -0.0037(6) 0.0108(6) O3 0.0864(11) 0.1111(14) 0.1321(17) 0.0743(13) -0.0260(12) -0.0298(11) _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 O1 1.433(2) . ? C1 C8 1.508(2) . ? C1 C2 1.548(2) . ? C1 H1 0.9800 . ? C2 O2 1.439(2) . ? C2 C14 1.504(3) . ? C2 H2 0.9800 . ? C3 O3 1.197(3) . ? C3 O2 1.362(3) . ? C3 C4 1.460(3) . ? C4 C5 1.492(3) . ? C4 C6 1.526(3) . ? C4 H4 0.9800 . ? C5 C6 1.486(3) . ? C5 H5A 0.9700 . ? C5 H5B 0.9700 . ? C6 C7 1.505(3) . ? C6 H6 0.9800 . ? C7 O1 1.440(2) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C8 C13 1.377(3) . ? C8 C9 1.381(3) . ? C9 C10 1.385(3) . ? C9 H9 0.9300 . ? C10 C11 1.375(4) . ? C10 H10 0.9300 . ? C11 C12 1.359(4) . ? C11 H11 0.9300 . ? C12 C13 1.389(3) . ? C12 H12 0.9300 . ? C13 H13 0.9300 . ? C14 C15 1.380(3) . ? C14 C19 1.386(3) . ? C15 C16 1.387(3) . ? C15 H15 0.9300 . ? C16 C17 1.370(4) . ? C16 H16 0.9300 . ? C17 C18 1.376(4) . ? C17 H17 0.9300 . ? C18 C19 1.385(3) . ? C18 H18 0.9300 . ? C19 H19 0.9300 . ? 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 O1 C1 C8 109.25(14) . . ? O1 C1 C2 109.07(14) . . ? C8 C1 C2 112.42(14) . . ? O1 C1 H1 108.7 . . ? C8 C1 H1 108.7 . . ? C2 C1 H1 108.7 . . ? O2 C2 C14 109.70(15) . . ? O2 C2 C1 105.16(14) . . ? C14 C2 C1 113.59(15) . . ? O2 C2 H2 109.4 . . ? C14 C2 H2 109.4 . . ? C1 C2 H2 109.4 . . ? O3 C3 O2 122.71(19) . . ? O3 C3 C4 124.9(2) . . ? O2 C3 C4 112.38(19) . . ? C3 C4 C5 122.6(2) . . ? C3 C4 C6 116.06(16) . . ? C5 C4 C6 59.00(15) . . ? C3 C4 H4 115.7 . . ? C5 C4 H4 115.7 . . ? C6 C4 H4 115.7 . . ? C6 C5 C4 61.63(15) . . ? C6 C5 H5A 117.6 . . ? C4 C5 H5A 117.6 . . ? C6 C5 H5B 117.6 . . ? C4 C5 H5B 117.6 . . ? H5A C5 H5B 114.7 . . ? C5 C6 C7 121.2(2) . . ? C5 C6 C4 59.37(15) . . ? C7 C6 C4 122.34(17) . . ? C5 C6 H6 114.3 . . ? C7 C6 H6 114.3 . . ? C4 C6 H6 114.3 . . ? O1 C7 C6 115.15(17) . . ? O1 C7 H7A 108.5 . . ? C6 C7 H7A 108.5 . . ? O1 C7 H7B 108.5 . . ? C6 C7 H7B 108.5 . . ? H7A C7 H7B 107.5 . . ? C13 C8 C9 118.4(2) . . ? C13 C8 C1 121.74(18) . . ? C9 C8 C1 119.85(19) . . ? C8 C9 C10 120.3(3) . . ? C8 C9 H9 119.8 . . ? C10 C9 H9 119.8 . . ? C11 C10 C9 120.3(3) . . ? C11 C10 H10 119.9 . . ? C9 C10 H10 119.9 . . ? C12 C11 C10 120.1(2) . . ? C12 C11 H11 120.0 . . ? C10 C11 H11 120.0 . . ? C11 C12 C13 119.6(3) . . ? C11 C12 H12 120.2 . . ? C13 C12 H12 120.2 . . ? C8 C13 C12 121.3(2) . . ? C8 C13 H13 119.4 . . ? C12 C13 H13 119.4 . . ? C15 C14 C19 119.0(2) . . ? C15 C14 C2 121.06(16) . . ? C19 C14 C2 119.9(2) . . ? C14 C15 C16 120.8(2) . . ? C14 C15 H15 119.6 . . ? C16 C15 H15 119.6 . . ? C17 C16 C15 119.7(3) . . ? C17 C16 H16 120.1 . . ? C15 C16 H16 120.1 . . ? C16 C17 C18 120.1(3) . . ? C16 C17 H17 119.9 . . ? C18 C17 H17 119.9 . . ? C17 C18 C19 120.3(2) . . ? C17 C18 H18 119.8 . . ? C19 C18 H18 119.8 . . ? C18 C19 C14 120.0(2) . . ? C18 C19 H19 120.0 . . ? C14 C19 H19 120.0 . . ? C1 O1 C7 114.89(16) . . ? C3 O2 C2 114.92(16) . . ? 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 C1 C2 O2 -42.15(18) . . . . ? C8 C1 C2 O2 -163.48(15) . . . . ? O1 C1 C2 C14 -162.11(14) . . . . ? C8 C1 C2 C14 76.56(19) . . . . ? O3 C3 C4 C5 166.4(2) . . . . ? O2 C3 C4 C5 -14.1(3) . . . . ? O3 C3 C4 C6 -125.2(3) . . . . ? O2 C3 C4 C6 54.3(3) . . . . ? C3 C4 C5 C6 103.0(2) . . . . ? C4 C5 C6 C7 -111.6(2) . . . . ? C3 C4 C6 C5 -113.9(3) . . . . ? C3 C4 C6 C7 -4.1(4) . . . . ? C5 C4 C6 C7 109.8(3) . . . . ? C5 C6 C7 O1 108.0(2) . . . . ? C4 C6 C7 O1 36.8(3) . . . . ? O1 C1 C8 C13 -70.1(2) . . . . ? C2 C1 C8 C13 51.1(2) . . . . ? O1 C1 C8 C9 108.0(2) . . . . ? C2 C1 C8 C9 -130.76(19) . . . . ? C13 C8 C9 C10 -1.3(3) . . . . ? C1 C8 C9 C10 -179.5(2) . . . . ? C8 C9 C10 C11 -0.1(4) . . . . ? C9 C10 C11 C12 1.5(4) . . . . ? C10 C11 C12 C13 -1.4(4) . . . . ? C9 C8 C13 C12 1.4(3) . . . . ? C1 C8 C13 C12 179.56(19) . . . . ? C11 C12 C13 C8 0.0(4) . . . . ? O2 C2 C14 C15 -34.3(2) . . . . ? C1 C2 C14 C15 83.0(2) . . . . ? O2 C2 C14 C19 146.32(17) . . . . ? C1 C2 C14 C19 -96.3(2) . . . . ? C19 C14 C15 C16 -1.3(3) . . . . ? C2 C14 C15 C16 179.4(2) . . . . ? C14 C15 C16 C17 1.6(4) . . . . ? C15 C16 C17 C18 -0.6(4) . . . . ? C16 C17 C18 C19 -0.7(4) . . . . ? C17 C18 C19 C14 1.0(4) . . . . ? C15 C14 C19 C18 0.0(3) . . . . ? C2 C14 C19 C18 179.35(19) . . . . ? C8 C1 O1 C7 -143.15(15) . . . . ? C2 C1 O1 C7 93.61(17) . . . . ? C6 C7 O1 C1 -120.9(2) . . . . ? O3 C3 O2 C2 40.9(3) . . . . ? C4 C3 O2 C2 -138.66(18) . . . . ? C14 C2 O2 C3 -148.08(15) . . . . ? C1 C2 O2 C3 89.41(17) . . . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.129 _refine_diff_density_min -0.226 _refine_diff_density_rms 0.049