Regiodivergent Oxidative Cross-Coupling of Catechols with Persistent tert-Carbon Radicals
Sugawara, Masumi; Ohnishi, Rikako; Ezawa, Tetsuya; Akakabe, Mai; Sawamura, Miki; Hojo, Daiki; Hashizume, Daisuke; Sohtome, Yoshihiro; Sodeoka, Mikiko; ACS Catalysis  (2020) 12770–12782; doi:10.1021/acscatal.0c03986

data_4518165
_publ_section_title
;
 Regiodivergent Oxidative Cross-Coupling of Catechols with Persistent
 tert-Carbon Radicals
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              12770
_journal_page_last               12782
_journal_paper_doi               10.1021/acscatal.0c03986
_journal_year                    2020
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C88 H66 O2 P4 Pd2, 2(B F4), 2(C4 H8 O2)'
_chemical_formula_sum            'C96 H82 B2 F8 O6 P4 Pd2'
_chemical_formula_weight         1841.91
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7004(2)
_cell_length_b                   20.3764(3)
_cell_length_c                   29.3278(5)
_cell_measurement_reflns_used    56811
_cell_measurement_temperature    90
_cell_measurement_theta_max      32.5930
_cell_measurement_theta_min      1.7440
_cell_volume                     8187.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_collection       CrystalClear
_computing_data_reduction        'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_molecular_graphics    SHELXLE
_computing_publication_material  'SHELXL-2018/1 (Sheldrick, 2018)'
_computing_structure_refinement  'SHELXL-2018/1 (Sheldrick, 2018)'
_computing_structure_solution    SHELXT-2014/5
_diffrn_ambient_temperature      90
_diffrn_detector_area_resol_mean 7.31
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Rigaku AFC-8 with Saturn70 CCD'
_diffrn_measurement_method       \w-scan
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0813
_diffrn_reflns_av_unetI/netI     0.0714
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            188450
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.659
_diffrn_reflns_theta_min         1.641
_diffrn_source                   'Fine-focus rotating anode'
_exptl_absorpt_coefficient_mu    0.593
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97618
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.39.9f (Rigaku Oxford Diffraction, 2015)
 Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.494
_exptl_crystal_description       block
_exptl_crystal_F_000             3760
_exptl_crystal_size_max          0.071
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.062
_refine_diff_density_max         0.757
_refine_diff_density_min         -0.588
_refine_diff_density_rms         0.093
_refine_ls_abs_structure_details
;
 Flack x determined using 8124 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.049(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1317
_refine_ls_number_reflns         28200
_refine_ls_number_restraints     679
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0492
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0410P)^2^+2.6071P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0910
_refine_ls_wR_factor_ref         0.0994
_reflns_Friedel_coverage         0.823
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.918
_reflns_number_gt                21952
_reflns_number_total             28200
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c03986_si_003.cif
_cod_data_source_block           MSU660-revised
_cod_database_code               4518165
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_min   0.959
_shelx_estimated_absorpt_t_max   0.964
_shelx_res_checksum              44039
_shelx_hkl_checksum              90693