Expansion of Azulenes as Nonbenzenoid Aromatic Compounds for C–H Activation: Rhodium- and Iridium-Catalyzed Oxidative Cyclization of Azulene Carboxylic Acids with Alkynes for the Synthesis of Azulenolactones and Benzoazulenes
Maeng, Chanyoung; Son, Jeong-Yu; Lee, Seung Cheol; Baek, Yonghyeon; Um, Kyusik; Han, Sang Hoon; Ko, Gi Hoon; Han, Gi Uk; Lee, Kyungsup; Lee, Kooyeon; Lee, Phil Ho; The Journal of Organic Chemistry  (2020) –; doi:10.1021/acs.joc.9b03448

data_4037910
_publ_section_title
;
 Expansion of Azulenes as Nonbenzenoid Aromatic Compounds for C--H
 Activation: Rhodium- and Iridium-Catalyzed Oxidative Cyclization of
 Azulene Carboxylic Acids with Alkynes for the Synthesis of
 Azulenolactones and Benzoazulenes
;
_journal_name_full               'The Journal of Organic Chemistry'
_journal_paper_doi               10.1021/acs.joc.9b03448
_journal_year                    2020
_chemical_formula_sum            'C41 H31 Cl2 N O4 S'
_chemical_formula_weight         704.63
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 92.99(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.916(3)
_cell_length_b                   13.548(3)
_cell_length_c                   18.394(4)
_cell_measurement_reflns_used    64419
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      33.575
_cell_measurement_theta_min      0.418
_cell_volume                     3463.2(13)
_computing_cell_refinement       HKL3000sm
_computing_data_collection       'PAL BL2D-SMDC Program'
_computing_data_reduction        HKL3000sm
_computing_structure_refinement  SHELXL
_computing_structure_solution    SHELXS
_diffrn_ambient_temperature      223(2)
_diffrn_measured_fraction_theta_full 0.945
_diffrn_measured_fraction_theta_max 0.960
_diffrn_measurement_device_type  'Rayonix MX225HS CCD area detector'
_diffrn_measurement_method       'omega scan'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.730
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_Laue_measured_fraction_full 0.945
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            31196
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        25.976
_diffrn_reflns_theta_max         29.999
_diffrn_reflns_theta_min         1.505
_diffrn_source                   'PLSII 2D bending magnet'
_exptl_absorpt_coefficient_mu    0.310
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.899
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'HKL3000sm Scalepack'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.351
_exptl_crystal_description       rod
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.088
_exptl_crystal_size_mid          0.041
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.464
_refine_diff_density_min         -0.929
_refine_diff_density_rms         0.107
_refine_ls_extinction_coef       0.0064(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     475
_refine_ls_number_reflns         8951
_refine_ls_number_restraints     119
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.1227
_refine_ls_R_factor_gt           0.0967
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2819
_refine_ls_wR_factor_ref         0.3061
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5791
_reflns_number_total             8951
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b03448_si_002.cif
_cod_data_source_block           PO16061O_014
_cod_original_cell_volume        3463.2(12)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               4037910
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.973
_shelx_estimated_absorpt_t_max   0.989
_shelx_res_checksum              91969
_shelx_hkl_checksum              7980