α-Diimine-mediated C-H functionalization of arenes for aryl-aryl cross-coupling reactions.
Babaguchi, Kotono; Bedi, Deepika; Chacon-Teran, Miguel A; Findlater, Michael; Organic & biomolecular chemistry 22 (2024) 2389–2394; doi:10.1039/d3ob01992f

data_7159794
_publ_section_title
;
 &#x3b1;-Diimine-mediated C-H functionalization of arenes for aryl-aryl
 cross-coupling reactions.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2389
_journal_page_last               2394
_journal_paper_doi               10.1039/d3ob01992f
_journal_volume                  22
_journal_year                    2024
_chemical_formula_moiety         'C40 H48 K N2 O6, C4 H10 O2'
_chemical_formula_sum            'C44 H58 K N2 O8'
_chemical_formula_weight         782.02
_chemical_name_systematic
'Potassium 2,6-dimethylBis(imino)acenaphthene 18-Crown-6'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-11-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-20 deposited with the CCDC.	2024-02-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.5169(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.87115(15)
_cell_length_b                   14.15084(13)
_cell_length_c                   17.71183(18)
_cell_measurement_reflns_used    49920
_cell_measurement_temperature    173
_cell_measurement_theta_max      79.5000
_cell_measurement_theta_min      2.6000
_cell_volume                     4228.37(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      173
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -75.00 -19.00   0.50    0.66    --  -91.75  61.00  30.00  112
  2  \w    -52.00 -20.00   0.50    0.66    --  -91.75  45.00  30.00   64
  3  \w    -52.00 -20.00   0.50    0.66    --  -91.75  45.00   0.00   64
  4  \w    -21.00  28.00   0.50    0.17    --  -47.81  19.00  30.00   98
  5  \w    -52.00 -20.00   0.50    0.66    --  -91.75  45.00 120.00   64
  6  \w    -52.00 -20.00   0.50    0.66    --  -91.75  45.00 -30.00   64
  7  \w    -52.00 -20.00   0.50    0.66    --  -91.75  45.00 -90.00   64
  8  \w    -85.00 -22.00   0.50    0.66    --  -91.75 125.00-180.00  126
  9  \w    -82.00 -23.00   0.50    0.66    --  -91.75 111.00-176.00  118
 10  \w    -82.00  -2.00   0.50    0.17    --  -47.81 111.00-176.00  160
 11  \w     24.00  85.00   0.50    0.17    --   47.81-111.00  89.00  122
 12  \w     45.00 108.00   0.50    0.66    --  113.25-111.00  89.00  126
 13  \w     42.00 106.00   0.50    0.66    --  113.25 -95.00 120.00  128
 14  \w     42.00 106.00   0.50    0.66    --  113.25 -95.00 -30.00  128
 15  \w     44.00 111.00   0.50    0.66    --  113.25-125.00-150.00  134
 16  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00 -90.00   58
 17  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00-120.00   58
 18  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00  60.00   58
 19  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00  90.00   58
 20  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00 120.00   58
 21  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00 150.00   58
 22  \w    -26.00  17.00   0.50    0.17    --   47.81 -19.00  30.00   86
 23  \w    -26.00  17.00   0.50    0.17    --   47.81 -19.00 -30.00   86
 24  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00-150.00   58
 25  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00 -60.00   58
 26  \w     42.00  71.00   0.50    0.66    --  113.25 -61.00   0.00   58
 27  \w     41.00 178.00   0.50    0.66    --  113.25   0.00  30.00  274
 28  \w    100.00 178.00   0.50    0.66    --  113.25  15.00-120.00  156
 29  \w    103.00 178.00   0.50    0.66    --  113.25 111.00-176.00  150
 30  \w     25.00 121.00   0.50    0.17    --   47.81  77.00 -90.00  192
 31  \w   -119.00 -33.00   0.50    0.17    --  -47.81 -57.00-120.00  172
 32  \w   -119.00 -25.00   0.50    0.17    --  -47.81 -77.00-180.00  188
 33  \w   -119.00 -25.00   0.50    0.17    --  -47.81 -77.00 -30.00  188
 34  \w   -119.00 -25.00   0.50    0.17    --  -47.81 -77.00   0.00  188
 35  \w   -119.00 -25.00   0.50    0.17    --  -47.81 -77.00  90.00  188
 36  \w   -119.00 -25.00   0.50    0.17    --  -47.81 -77.00 120.00  188
 37  \w   -163.00-135.00   0.50    0.66    --  -91.75 -61.00  90.00   56
 38  \w   -163.00 -69.00   0.50    0.66    --  -91.75 -77.00  60.00  188
 39  \w   -163.00 -69.00   0.50    0.66    --  -91.75 -77.00   0.00  188
 40  \w   -163.00 -75.00   0.50    0.66    --  -91.75 -61.00 120.00  176
 41  \w   -163.00 -69.00   0.50    0.66    --  -91.75 -77.00 -60.00  188
 42  \w   -163.00 -69.00   0.50    0.66    --  -91.75 -77.00-120.00  188
 43  \w   -163.00 -69.00   0.50    0.66    --  -91.75 -77.00-180.00  188
 44  \w   -163.00 -83.00   0.50    0.66    --  -91.75 -95.00-150.00  160
 45  \w   -160.00 -81.00   0.50    0.66    --  -91.75-111.00  89.00  158
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0619539000
_diffrn_orient_matrix_UB_12      -0.0778184000
_diffrn_orient_matrix_UB_13      -0.0143410000
_diffrn_orient_matrix_UB_21      0.0670962000
_diffrn_orient_matrix_UB_22      0.0727314000
_diffrn_orient_matrix_UB_23      0.0111071000
_diffrn_orient_matrix_UB_31      0.0025816000
_diffrn_orient_matrix_UB_32      -0.0225668000
_diffrn_orient_matrix_UB_33      0.0850167000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0529
_diffrn_reflns_av_unetI/netI     0.0228
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            83389
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.755
_diffrn_reflns_theta_min         2.619
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.530
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20079
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.228
_exptl_crystal_description       needle
_exptl_crystal_F_000             1676
_exptl_crystal_preparation
'In a 20 mL reaction vial, 2,6-dimethylBis(imino)acenaphthene, Potassium tert-butoxide, and 18-Crown-6 were charged under an inert atmosphere. To the mixture was added 1 mL of Diethyl ether and a few drops of 1,2-Dimethoxyethane followed by stirring for 20 min. After that, the stir bar was removed, and the solution was kept unperturbed at -35 Celsius degree.'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether and 1,2-dimethoxyethane'
_refine_diff_density_max         0.763
_refine_diff_density_min         -0.594
_refine_diff_density_rms         0.056
_refine_ls_extinction_coef       0.00016(6)
_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   1.043
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     511
_refine_ls_number_reflns         8949
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0502
_refine_ls_R_factor_gt           0.0478
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0529P)^2^+4.5156P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1262
_refine_ls_wR_factor_ref         0.1278
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8350
_reflns_number_total             8949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob01992f2.cif
_cod_data_source_block           kb1196_3_auto
_cod_depositor_comments          'Adding full bibliography for 7159794.cif.'
_cod_database_code               7159794
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C32 H34 N2 O2 K'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C10(H10A,H10B), C13(H13A,H13B), C16(H16A,H16B), C7(H7A,H7B),
 C9(H9A,H9B), C12(H12A,H12B), C4(H4A,H4B), C19(H19A,H19B), C18(H18A,H18B),
 C15(H15A,H15B), C51(H51A,H51B), C52(H52A,H52B)
2.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C37(H37), C35(H35), C36(H36), C28(H28), C23(H23), C27(H27),
 C46(H46), C44(H44), C45(H45), C25(H25), C24(H24)
2.c Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C39(H39A,H39B,H39C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C)
;
_shelx_res_checksum              68981
_olex2_submission_original_sample_id KB1196_3
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.789
_oxdiff_exptl_absorpt_empirical_full_min 0.509