Enantioselective electrosynthesis of inherently chiral calix[4]arenes via a cobalt-catalyzed aryl C–H acyloxylation
Zhang, Liming; Yang, Chen; Wang, Xinhai; Yang, Taixin; Yang, Dandan; Dou, Yingchao; Niu, Jun-Long; Green Chemistry 26 (2024) 10232–10239; doi:10.1039/D4GC02877E

data_7249290
_publ_section_title
;
 Enantioselective electrosynthesis of inherently chiral calix[4]arenes via
 a cobalt-catalyzed aryl C--H acyloxylation
;
_journal_issue                   19
_journal_name_full               'Green Chemistry'
_journal_page_first              10232
_journal_page_last               10239
_journal_paper_doi               10.1039/D4GC02877E
_journal_volume                  26
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C54 H65 N2 O8'
_chemical_formula_sum            'C54 H65 N2 O8'
_chemical_formula_weight         870.08
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-10
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-03-13 deposited with the CCDC.	2024-08-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7335(2)
_cell_length_b                   13.0898(4)
_cell_length_c                   38.4467(11)
_cell_measurement_reflns_used    15805
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      72.9340
_cell_measurement_theta_min      3.5490
_cell_volume                     4898.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -81.00 -38.00   0.50    0.50    --    0.00 -57.00   0.00   86
  2  \w    -89.00  16.00   0.50    0.50    --    0.00 -38.00-120.00  210
  3  \w     60.00  85.00   0.50    0.50    --    0.00  38.00-120.00   50
  4  \w    -21.00  38.00   0.50    0.50    --    0.00  38.00-120.00  118
  5  \w    -17.00  25.00   0.50    0.50    --    0.00 -57.00   0.00   84
  6  \w     51.00  76.00   0.50    0.50    --    0.00  38.00 -90.00   50
  7  \w      8.00 119.00   0.50    7.00    --   96.90 -61.00   0.00  222
  8  \w     27.00 131.00   0.50    7.00    --   96.90 -82.00 -90.00  208
  9  \w     25.00  79.00   0.50    7.00    --   96.90 -30.00 120.00  108
 10  \w    139.00 185.00   0.50    7.00    --   96.90  45.00-150.00   92
 11  \w     10.00 131.00   0.50    7.00    --   96.90 -82.00 120.00  242
 12  \w    139.00 185.00   0.50    7.00    --   96.90  15.00 120.00   92
 13  \w      8.00 122.00   0.50    7.00    --   96.90 -61.00 -90.00  228
 14  \w     49.00 126.00   0.50    7.00    --   96.90 -82.00  30.00  154
 15  \w     77.00 103.00   0.50    7.00    --   96.90 -82.00-150.00   52
 16  \w     61.00 184.00   0.50    7.00    --   96.90  15.00-120.00  246
 17  \w     40.00  74.00   0.50    7.00    --   96.90 -82.00-150.00   68
 18  \w     61.00 185.00   0.50    7.00    --   96.90  15.00-180.00  248
 19  \w     78.00 103.00   0.50    7.00    --   96.90 -82.00 -30.00   50
 20  \w     93.00 118.00   0.50    7.00    --   96.90 -30.00 120.00   50
 21  \w    146.00 178.00   0.50    7.00    --   96.90  82.00  90.00   64
 22  \w     61.00  98.00   0.50    7.00    --   96.90 -82.00-180.00   74
 23  \w     77.00 102.00   0.50    7.00    --   96.90 -82.00 -60.00   50
 24  \w     46.00 101.00   0.50    7.00    --   96.90 -82.00 150.00  110
 25  \w     87.00 112.00   0.50    7.00    --   96.90  82.00  90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0614632000
_diffrn_orient_matrix_UB_12      -0.0764220000
_diffrn_orient_matrix_UB_13      -0.0261906000
_diffrn_orient_matrix_UB_21      0.0438493000
_diffrn_orient_matrix_UB_22      -0.0892998000
_diffrn_orient_matrix_UB_23      0.0236028000
_diffrn_orient_matrix_UB_31      -0.1391701000
_diffrn_orient_matrix_UB_32      0.0055472000
_diffrn_orient_matrix_UB_33      0.0190291000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0611
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            54476
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.597
_diffrn_reflns_theta_min         3.567
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.627
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45677
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.180
_exptl_crystal_description       block
_exptl_crystal_F_000             1868
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.585
_refine_diff_density_min         -0.470
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 3233 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     583
_refine_ls_number_reflns         9828
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0666
_refine_ls_R_factor_gt           0.0552
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0993P)^2^+1.0275P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1530
_refine_ls_wR_factor_ref         0.1636
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.967
_reflns_number_gt                8384
_reflns_number_total             9828
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4gc02877e2.cif
_cod_data_source_block           exp_20437_1_200_00
_cod_depositor_comments          'Adding full bibliography for 7249290.cif.'
_cod_database_code               7249290
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.885
_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 Ternary CH refined with riding coordinates:
 C30(H30)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C21(H21A,H21B), C28(H28A,H28B), C31(H31A,H31B),
 C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C43(H43A,H43B), C44(H44A,H44B),
  C46(H46A,H46B), C47(H47A,H47B), C49(H49A,H49B), C50(H50A,H50B), C52(H52A,
 H52B), C53(H53A,H53B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C11(H11), C12(H12), C13(H13), C18(H18), C19(H19), C20(H20), C25(H25),
 C26(H26), C27(H27), C39(H39), C40(H40), C41(H41), C42(H42)
2.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C36(H36A,H36B,H36C), C45(H45A,H45B,H45C), C48(H48A,H48B,
 H48C), C51(H51A,H51B,H51C), C54(H54A,H54B,H54C)
;
_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 1.819
_oxdiff_exptl_absorpt_empirical_full_min 0.560