# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Keisuke Kato' _publ_contact_author_email KKK@PHAR.TOHO-U.AC.JP _publ_section_title ; meso-Phbox-Pd(II) Catalyzed Tandem Carbonylative Cyclization of 1-Ethynyl-1-propargyl Acetate ; _journal_coden_ASTM ? _journal_coeditor_code ? _journal_coeditor_name ? _journal_coeditor_notes ; ? ; _journal_date_accepted ? _journal_date_from_coeditor ? _journal_date_printers_final ? _journal_date_printers_first ? _journal_date_proofs_in ? _journal_date_proofs_out ? #======================================================================== # PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_issue ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? _journal_techeditor_code ? _journal_techeditor_notes ; ? ; loop_ _publ_author_name 'Keisuke Kato' 'Hiroyuki Akita' 'Takeo Fujinami' 'Takuya Kobayashi' 'Taichi Kusakabe' 'Tomoyuki Mochida' ; S.Motodate ; # Attachment 'kato1.cif' data_kato1 _database_code_depnum_ccdc_archive 'CCDC 685066' _audit_creation_method SHELXL-97 _chemical_name_systematic '05 January 2008' _publ_section_exptl_refinement ; All H atoms were observable in a difference Fourier map. However, except for the hydroxyl H atom, all other satoms were placed in geometrically idealised positions and constrained to ride on their parent atoms with C---H distances in the range 0.93-0.97 \%A and U~iso~(H) = 1.2U~eq~(C). The hydroxyl H atom was constrained to an ideal geometry with O--H distance of 0.82 \%A and U~iso~(H) = 1.5U~eq~(O), but the group was allowed to rotate freely about its O---C bond. ; _chemical_name_common '05 January 2008' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C16 H14 O4' _chemical_formula_weight 270.27 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' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21 / n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.1176(7) _cell_length_b 8.1836(9) _cell_length_c 25.614(3) _cell_angle_alpha 90.00 _cell_angle_beta 93.427(2) _cell_angle_gamma 90.00 _cell_volume 1280.1(2) _cell_formula_units_Z 4 _cell_measurement_temperature 100(1) _cell_measurement_reflns_used 2570 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 27.81 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.402 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 568 _exptl_absorpt_coefficient_mu 0.101 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.9811 _exptl_absorpt_correction_T_max 0.9947 _exptl_absorpt_process_details 'SADABS Sheldrick 1996' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(1) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker APEX II CCD diffractometer' _diffrn_measurement_method '\f and \w scans' _diffrn_detector_area_resol_mean 8.366 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8167 _diffrn_reflns_av_R_equivalents 0.0238 _diffrn_reflns_av_sigmaI/netI 0.0292 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -7 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 1.59 _diffrn_reflns_theta_max 27.90 _reflns_number_total 3045 _reflns_number_gt 2503 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 (Bruker--Nonius, 2004)' _computing_cell_refinement 'APEX2 (Bruker--Nonius, 2004)' _computing_data_reduction 'SAINT-Plus (Bruker--Nonius, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEPIII (Burnett et al.,)' _computing_publication_material 'SHELXL97 and PLATON' _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^)+(0.0480P)^2^+0.5587P] 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 3045 _refine_ls_number_parameters 182 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0522 _refine_ls_R_factor_gt 0.0398 _refine_ls_wR_factor_ref 0.1028 _refine_ls_wR_factor_gt 0.0951 _refine_ls_goodness_of_fit_ref 1.014 _refine_ls_restrained_S_all 1.014 _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 C2 C 0.7249(2) 0.23897(16) 0.14670(5) 0.0179(3) Uani 1 1 d . . . H2 H 0.7545 0.3014 0.1176 0.021 Uiso 1 1 calc R . . C13 C 0.5288(2) 0.83208(16) 0.06193(5) 0.0151(3) Uani 1 1 d . . . C8 C 0.4602(2) 0.55497(16) 0.14099(5) 0.0158(3) Uani 1 1 d . . . H8A H 0.5667 0.5442 0.1146 0.019 Uiso 1 1 calc R . . H8B H 0.5377 0.5913 0.1730 0.019 Uiso 1 1 calc R . . C7 C 0.3607(2) 0.38702(16) 0.15050(5) 0.0164(3) Uani 1 1 d . . . H7A H 0.2488 0.3982 0.1755 0.020 Uiso 1 1 calc R . . H7B H 0.2904 0.3474 0.1180 0.020 Uiso 1 1 calc R . . C10 C 0.1565(2) 0.62863(16) 0.07422(5) 0.0156(3) Uani 1 1 d . . . C9 C 0.2923(2) 0.68705(16) 0.12310(5) 0.0152(3) Uani 1 1 d . . . C6 C 0.4881(2) 0.16555(17) 0.21413(5) 0.0178(3) Uani 1 1 d . . . H6 H 0.3579 0.1787 0.2306 0.021 Uiso 1 1 calc R . . C14 C 0.7333(2) 0.84114(17) -0.00934(5) 0.0178(3) Uani 1 1 d . . . C1 C 0.5280(2) 0.26186(15) 0.17087(5) 0.0151(3) Uani 1 1 d . . . C5 C 0.6399(2) 0.04994(17) 0.23304(5) 0.0213(3) Uani 1 1 d . . . H5 H 0.6105 -0.0134 0.2619 0.026 Uiso 1 1 calc R . . C12 C 0.4371(2) 0.72390(16) 0.02109(5) 0.0146(3) Uani 1 1 d . . . C11 C 0.2595(2) 0.63049(16) 0.02425(5) 0.0167(3) Uani 1 1 d . . . H11 H 0.2038 0.5693 -0.0041 0.020 Uiso 1 1 calc R . . C16 C 0.4132(2) 0.84696(16) 0.11135(5) 0.0167(3) Uani 1 1 d . . . H16A H 0.3089 0.9362 0.1082 0.020 Uiso 1 1 calc R . . H16B H 0.5185 0.8717 0.1401 0.020 Uiso 1 1 calc R . . C15 C 0.7060(2) 0.90333(16) 0.04375(5) 0.0175(3) Uani 1 1 d . . . H15 H 0.7961 0.9789 0.0616 0.021 Uiso 1 1 calc R . . C3 C 0.8768(2) 0.12383(17) 0.16575(6) 0.0202(3) Uani 1 1 d . . . H3 H 1.0073 0.1103 0.1494 0.024 Uiso 1 1 calc R . . C4 C 0.8349(2) 0.02907(17) 0.20889(6) 0.0216(3) Uani 1 1 d . . . H4 H 0.9368 -0.0478 0.2215 0.026 Uiso 1 1 calc R . . O1 O 0.15011(16) 0.71879(13) 0.16348(4) 0.0218(2) Uani 1 1 d . . . H1 H 0.0320 0.6739 0.1566 0.033 Uiso 1 1 calc R . . O3 O 0.55950(15) 0.73319(11) -0.02205(4) 0.0176(2) Uani 1 1 d . . . O2 O -0.03069(15) 0.57918(12) 0.07838(4) 0.0217(2) Uani 1 1 d . . . O4 O 0.86795(16) 0.86621(13) -0.04042(4) 0.0244(2) 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 C2 0.0211(7) 0.0162(6) 0.0166(6) 0.0012(5) 0.0025(5) -0.0014(5) C13 0.0175(6) 0.0105(6) 0.0169(6) 0.0018(5) -0.0007(5) 0.0027(5) C8 0.0154(6) 0.0162(6) 0.0156(6) 0.0015(5) 0.0001(5) 0.0003(5) C7 0.0158(6) 0.0162(6) 0.0173(6) 0.0012(5) 0.0023(5) 0.0006(5) C10 0.0146(6) 0.0123(6) 0.0199(7) 0.0029(5) 0.0008(5) 0.0029(5) C9 0.0160(6) 0.0165(6) 0.0135(6) 0.0005(5) 0.0034(5) 0.0014(5) C6 0.0193(7) 0.0187(7) 0.0156(6) -0.0014(5) 0.0027(5) -0.0020(5) C14 0.0172(6) 0.0155(6) 0.0206(7) 0.0029(5) 0.0004(5) 0.0007(5) C1 0.0174(6) 0.0131(6) 0.0147(6) -0.0013(5) 0.0002(5) -0.0013(5) C5 0.0306(8) 0.0192(7) 0.0137(6) 0.0026(5) -0.0005(5) -0.0009(6) C12 0.0159(6) 0.0144(6) 0.0138(6) 0.0019(5) 0.0027(5) 0.0036(5) C11 0.0177(6) 0.0166(6) 0.0154(6) -0.0013(5) -0.0014(5) 0.0006(5) C16 0.0207(7) 0.0140(6) 0.0156(6) -0.0015(5) 0.0023(5) 0.0005(5) C15 0.0194(6) 0.0149(6) 0.0181(7) 0.0010(5) -0.0002(5) -0.0011(5) C3 0.0185(6) 0.0195(7) 0.0227(7) -0.0038(5) 0.0016(5) 0.0006(5) C4 0.0257(7) 0.0173(7) 0.0210(7) -0.0002(5) -0.0055(6) 0.0041(5) O1 0.0212(5) 0.0256(5) 0.0195(5) -0.0022(4) 0.0085(4) 0.0007(4) O3 0.0188(5) 0.0184(5) 0.0158(5) -0.0003(4) 0.0040(4) -0.0019(4) O2 0.0143(5) 0.0255(5) 0.0252(5) 0.0027(4) 0.0010(4) -0.0012(4) O4 0.0230(5) 0.0276(6) 0.0235(5) 0.0026(4) 0.0080(4) -0.0028(4) _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 C2 C3 1.3911(19) . ? C2 C1 1.3995(18) . ? C2 H2 0.9300 . ? C13 C15 1.3387(18) . ? C13 C12 1.4570(18) . ? C13 C16 1.4914(18) . ? C8 C7 1.5286(18) . ? C8 C9 1.5419(18) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? C7 C1 1.5183(18) . ? C7 H7A 0.9700 . ? C7 H7B 0.9700 . ? C10 O2 1.2250(16) . ? C10 C11 1.4601(18) . ? C10 C9 1.5369(19) . ? C9 O1 1.4147(15) . ? C9 C16 1.5418(18) . ? C6 C5 1.392(2) . ? C6 C1 1.3932(18) . ? C6 H6 0.9300 . ? C14 O4 1.1969(16) . ? C14 O3 1.4056(16) . ? C14 C15 1.4710(19) . ? C5 C4 1.387(2) . ? C5 H5 0.9300 . ? C12 C11 1.3350(18) . ? C12 O3 1.3736(15) . ? C11 H11 0.9300 . ? C16 H16A 0.9700 . ? C16 H16B 0.9700 . ? C15 H15 0.9300 . ? C3 C4 1.386(2) . ? C3 H3 0.9300 . ? C4 H4 0.9300 . ? O1 H1 0.8200 . ? 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 C3 C2 C1 120.66(12) . . ? C3 C2 H2 119.7 . . ? C1 C2 H2 119.7 . . ? C15 C13 C12 107.47(12) . . ? C15 C13 C16 133.99(13) . . ? C12 C13 C16 118.49(11) . . ? C7 C8 C9 114.39(11) . . ? C7 C8 H8A 108.7 . . ? C9 C8 H8A 108.7 . . ? C7 C8 H8B 108.7 . . ? C9 C8 H8B 108.7 . . ? H8A C8 H8B 107.6 . . ? C1 C7 C8 113.24(11) . . ? C1 C7 H7A 108.9 . . ? C8 C7 H7A 108.9 . . ? C1 C7 H7B 108.9 . . ? C8 C7 H7B 108.9 . . ? H7A C7 H7B 107.7 . . ? O2 C10 C11 122.30(12) . . ? O2 C10 C9 119.63(12) . . ? C11 C10 C9 118.05(11) . . ? O1 C9 C10 109.07(10) . . ? O1 C9 C16 108.07(10) . . ? C10 C9 C16 110.32(11) . . ? O1 C9 C8 109.83(10) . . ? C10 C9 C8 110.01(11) . . ? C16 C9 C8 109.51(10) . . ? C5 C6 C1 121.06(13) . . ? C5 C6 H6 119.5 . . ? C1 C6 H6 119.5 . . ? O4 C14 O3 119.66(12) . . ? O4 C14 C15 132.55(13) . . ? O3 C14 C15 107.79(11) . . ? C6 C1 C2 118.20(12) . . ? C6 C1 C7 120.56(12) . . ? C2 C1 C7 121.24(11) . . ? C4 C5 C6 120.16(13) . . ? C4 C5 H5 119.9 . . ? C6 C5 H5 119.9 . . ? C11 C12 O3 124.42(12) . . ? C11 C12 C13 125.76(12) . . ? O3 C12 C13 109.81(11) . . ? C12 C11 C10 117.04(12) . . ? C12 C11 H11 121.5 . . ? C10 C11 H11 121.5 . . ? C13 C16 C9 110.73(11) . . ? C13 C16 H16A 109.5 . . ? C9 C16 H16A 109.5 . . ? C13 C16 H16B 109.5 . . ? C9 C16 H16B 109.5 . . ? H16A C16 H16B 108.1 . . ? C13 C15 C14 108.05(12) . . ? C13 C15 H15 126.0 . . ? C14 C15 H15 126.0 . . ? C4 C3 C2 120.49(13) . . ? C4 C3 H3 119.8 . . ? C2 C3 H3 119.8 . . ? C3 C4 C5 119.43(13) . . ? C3 C4 H4 120.3 . . ? C5 C4 H4 120.3 . . ? C9 O1 H1 109.5 . . ? C12 O3 C14 106.84(10) . . ? 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 C9 C8 C7 C1 -176.88(11) . . . . ? O2 C10 C9 O1 -17.58(16) . . . . ? C11 C10 C9 O1 164.00(11) . . . . ? O2 C10 C9 C16 -136.13(12) . . . . ? C11 C10 C9 C16 45.45(15) . . . . ? O2 C10 C9 C8 102.95(13) . . . . ? C11 C10 C9 C8 -75.47(14) . . . . ? C7 C8 C9 O1 65.18(14) . . . . ? C7 C8 C9 C10 -54.89(14) . . . . ? C7 C8 C9 C16 -176.30(11) . . . . ? C5 C6 C1 C2 0.2(2) . . . . ? C5 C6 C1 C7 179.74(13) . . . . ? C3 C2 C1 C6 -0.47(19) . . . . ? C3 C2 C1 C7 -179.98(13) . . . . ? C8 C7 C1 C6 131.59(13) . . . . ? C8 C7 C1 C2 -48.92(17) . . . . ? C1 C6 C5 C4 0.1(2) . . . . ? C15 C13 C12 C11 179.80(13) . . . . ? C16 C13 C12 C11 -2.4(2) . . . . ? C15 C13 C12 O3 -0.94(15) . . . . ? C16 C13 C12 O3 176.90(11) . . . . ? O3 C12 C11 C10 176.63(11) . . . . ? C13 C12 C11 C10 -4.2(2) . . . . ? O2 C10 C11 C12 162.98(13) . . . . ? C9 C10 C11 C12 -18.64(18) . . . . ? C15 C13 C16 C9 -153.05(15) . . . . ? C12 C13 C16 C9 29.82(16) . . . . ? O1 C9 C16 C13 -167.85(11) . . . . ? C10 C9 C16 C13 -48.68(14) . . . . ? C8 C9 C16 C13 72.54(14) . . . . ? C12 C13 C15 C14 -0.45(15) . . . . ? C16 C13 C15 C14 -177.81(14) . . . . ? O4 C14 C15 C13 -178.44(15) . . . . ? O3 C14 C15 C13 1.66(15) . . . . ? C1 C2 C3 C4 0.4(2) . . . . ? C2 C3 C4 C5 0.0(2) . . . . ? C6 C5 C4 C3 -0.2(2) . . . . ? C11 C12 O3 C14 -178.76(13) . . . . ? C13 C12 O3 C14 1.96(13) . . . . ? O4 C14 O3 C12 177.89(12) . . . . ? C15 C14 O3 C12 -2.20(13) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 27.90 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.343 _refine_diff_density_min -0.233 _refine_diff_density_rms 0.052