Copper-catalyzed chemoselective C-H functionalization/dearomatization sequence: direct access to indole-based spirocyclic scaffolds.
Zhao, Yuting; Ji, Xin; Xiao, Yuanjing; Wu, Xingxing; Liu, Lu; Chemical communications (Cambridge, England) 61 (2025) 5162–5165; doi:10.1039/d5cc00594a

data_7134297
_publ_section_title
;
 Copper-catalyzed chemoselective C-H functionalization/dearomatization
 sequence: direct access to indole-based spirocyclic scaffolds.
;
_journal_issue                   27
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5162
_journal_page_last               5165
_journal_paper_doi               10.1039/d5cc00594a
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C28 H26 Br N O'
_chemical_formula_sum            'C28 H26 Br N O'
_chemical_formula_weight         472.41
_chemical_melting_point          399
_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             2024-04-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-11 deposited with the CCDC.	2025-03-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.45840(10)
_cell_length_b                   15.99770(10)
_cell_length_c                   18.87770(10)
_cell_measurement_reflns_used    71296
_cell_measurement_temperature    169.99(10)
_cell_measurement_theta_max      73.5030
_cell_measurement_theta_min      3.6150
_cell_volume                     4668.43(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.100a (Rigaku OD, 2023)'
_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      169.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -29.00  -3.00   1.00    1.00    --    0.00 -63.00 126.00   26
  2  \w     42.00 120.00   1.00    1.00    --   92.10 -63.00 126.00   78
  3  \w     64.00  89.00   1.00    1.00    --   92.10  63.00 -96.00   25
  4  \w      3.00  38.00   1.00    1.00    --   92.10 -63.00 126.00   35
  5  \w    -27.00   8.00   1.00    1.00    --    0.00  57.00-120.00   35
  6  \w    -16.00  89.00   1.00    1.00    --    0.00  77.00-180.00  105
  7  \w    -27.00  88.00   1.00    1.00    --    0.00  63.00 -96.00  115
  8  \w     17.00  55.00   1.00    1.00    --    0.00  57.00-120.00   38
  9  \w    -25.00  13.00   1.00    1.00    --    0.00  57.00 -30.00   38
 10  \w    -27.00  62.00   1.00    1.00    --    0.00  37.00  30.00   89
 11  \w    -27.00  82.00   1.00    1.00    --    0.00  57.00 150.00  109
 12  \w    -27.00  54.00   1.00    1.00    --    0.00  37.00 120.00   81
 13  \w     20.00  68.00   1.00    1.00    --    0.00  57.00 -30.00   48
 14  \w     79.00 105.00   1.00    1.00    --   92.10 -82.00 -30.00   26
 15  \w     57.00  88.00   1.00    1.00    --   92.10  82.00 150.00   31
 16  \w     58.00  90.00   1.00    1.00    --   92.10  80.00 -19.77   32
 17  \w     57.00  83.00   1.00    1.00    --   92.10  82.00  85.24   26
 18  \w    106.00 181.00   1.00    1.00    --   92.10  82.00  85.24   75
 19  \w      5.00  68.00   1.00    1.00    --   92.10 -82.00 -30.00   63
 20  \w     59.00  84.00   1.00    1.00    --   92.10  77.00 120.00   25
 21  \w     57.00  82.00   1.00    1.00    --   92.10  82.00 -90.00   25
 22  \w     59.00  84.00   1.00    1.00    --   92.10  76.00 141.31   25
 23  \w     58.00 165.00   1.00    1.00    --   92.10  79.00  51.51  107
 24  \w     59.00  84.00   1.00    1.00    --   92.10  77.00  -0.94   25
 25  \w    111.00 137.00   1.00    1.00    --   92.10  76.00 141.31   26
 26  \w     63.00 181.00   1.00    1.00    --   92.10  64.00 -44.10  118
 27  \w     57.00  82.00   1.00    1.00    --   92.10  82.00   0.00   25
 28  \w     57.00 182.00   1.00    1.00    --   92.10  82.00  66.91  125
 29  \w     59.00  84.00   1.00    1.00    --   92.10  77.00-180.00   25
 30  \w     57.00  82.00   1.00    1.00    --   92.10  82.00  30.00   25
 31  \w    104.00 140.00   1.00    1.00    --   92.10  82.00  30.00   36
 32  \w     59.00 174.00   1.00    1.00    --   92.10  77.00 -30.00  115
 33  \w     59.00  85.00   1.00    1.00    --   92.10  77.00 150.00   26
 34  \w     60.00  85.00   1.00    1.00    --   92.10  75.00  27.13   25
 35  \w     57.00  82.00   1.00    1.00    --   92.10  82.00-180.00   25
 36  \w     59.00  84.00   1.00    1.00    --   92.10  76.00 -39.70   25
 37  \w     59.00  85.00   1.00    1.00    --   92.10  77.00 -60.00   26
 38  \w     57.00  83.00   1.00    1.00    --   92.10  82.00-150.00   26
 39  \w     85.00 128.00   1.00    1.00    --   92.10 -82.00-120.00   43
 40  \w      5.00 128.00   1.00    1.00    --   92.10 -82.00 120.00  123
 41  \w     64.00 181.00   1.00    1.00    --   92.10  61.00  30.00  117
 42  \w     64.00  89.00   1.00    1.00    --   92.10  62.00-161.47   25
 43  \w    123.00 181.00   1.00    1.00    --   92.10  62.00-161.47   58
 44  \w     61.00  87.00   1.00    1.00    --   92.10  73.00-148.00   26
 45  \w    116.00 158.00   1.00    1.00    --   92.10  73.00-148.00   42
 46  \w     66.00 166.00   1.00    1.00    --   92.10  45.00  30.00  100
 47  \w     57.00  82.00   1.00    1.00    --   92.10  82.00-120.00   25
 48  \w     58.00  84.00   1.00    1.00    --   92.10  82.00 -60.00   26
 49  \w     66.00 181.00   1.00    1.00    --   92.10  40.00 -70.83  115
 50  \w     65.00  91.00   1.00    1.00    --   92.10  55.00 150.96   26
 51  \w     57.00  82.00   1.00    1.00    --   92.10  82.00  60.00   25
 52  \w     57.00  83.00   1.00    1.00    --   92.10  82.00  90.00   26
 53  \w      3.00 119.00   1.00    1.00    --   92.10 -61.00   0.00  116
 54  \w     57.00  83.00   1.00    1.00    --   92.10  82.00-112.65   26
 55  \w     66.00  92.00   1.00    1.00    --   92.10  45.00 120.00   26
 56  \w     66.00 114.00   1.00    1.00    --   92.10  44.00 -46.79   48
 57  \w     66.00 167.00   1.00    1.00    --   92.10  50.00-117.07  101
 58  \w     86.00 128.00   1.00    1.00    --   92.10 -82.00-180.00   42
 59  \w      7.00  45.00   1.00    1.00    --   92.10 -82.00  30.00   38
 60  \w     46.00  72.00   1.00    1.00    --   92.10 -82.00-120.00   26
 61  \w     65.00  90.00   1.00    1.00    --   92.10  56.00-138.90   25
 62  \w     67.00 115.00   1.00    1.00    --   92.10  45.00-150.00   48
 63  \w     66.00  91.00   1.00    1.00    --   92.10  46.00 159.32   25
 64  \w     67.00  92.00   1.00    1.00    --   92.10  46.00 134.14   25
 65  \w     47.00  72.00   1.00    1.00    --   92.10 -82.00 -90.00   25
 66  \w     83.00 125.00   1.00    1.00    --   92.10 -82.00 -90.00   42
 67  \w     66.00 181.00   1.00    1.00    --   92.10  52.00 170.92  115
 68  \w     59.00  84.00   1.00    1.00    --   92.10  77.00 -90.00   25
 69  \w     57.00  83.00   1.00    1.00    --   92.10  81.00-137.12   26
 70  \w     64.00  97.00   1.00    1.00    --   92.10  61.00-120.00   33
 71  \w    114.00 140.00   1.00    1.00    --   92.10  77.00 120.00   26
 72  \w     56.00 123.00   1.00    1.00    --   92.10 -82.00  30.00   67
 73  \w    123.00 149.00   1.00    1.00    --   92.10  63.00 -96.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0496642000
_diffrn_orient_matrix_UB_12      -0.0476559000
_diffrn_orient_matrix_UB_13      0.0581044000
_diffrn_orient_matrix_UB_21      0.0543053000
_diffrn_orient_matrix_UB_22      0.0787220000
_diffrn_orient_matrix_UB_23      0.0152300000
_diffrn_orient_matrix_UB_31      -0.0672114000
_diffrn_orient_matrix_UB_32      0.0283554000
_diffrn_orient_matrix_UB_33      0.0552434000
_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  0.0567
_diffrn_reflns_av_unetI/netI     0.0191
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            133994
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         3.622
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.538
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61472
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.100a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             1952
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: PE/DCM'
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.478
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 3568 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.020(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     561
_refine_ls_number_reflns         8340
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0236
_refine_ls_R_factor_gt           0.0230
_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^)+(0.0303P)^2^+1.6197P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0596
_refine_ls_wR_factor_ref         0.0600
_reflns_Friedel_coverage         0.802
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                8138
_reflns_number_total             8340
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc00594a2.cif
_cod_data_source_block           exp_4174_auto
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '399K' was changed to '399'
-- the value should be numeric and without a unit designator.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7134297.cif.
;
_cod_database_code               7134297
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C12(H12), C35(H35), C50(H50)
2.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C46(H46A,H46B), C47(H47A,
 H47B), C48(H48A,H48B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C4(H4), C5(H5), C9(H9), C14(H14), C15(H15), C16(H16),
  C17(H17), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), N2(H2A), C30(H30),
  C31(H31), C33(H33), C34(H34), C38(H38), C41(H41), C42(H42), C43(H43),
 C44(H44), C52(H52), C53(H53), C54(H54), C55(H55), C56(H56)
2.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C49(H49A,H49B,H49C)
;
_shelx_res_checksum              44951
_shelx_hkl_checksum              52809
_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 1.439
_oxdiff_exptl_absorpt_empirical_full_min 0.741