Oxidative rearrangement of indoles mediated by 2-bromoethanol and hydrogen peroxide to access spirooxindoles.
Xiao, Dan; Shi, Haofeng; He, Jiaxin; Yang, Kaiyue; Yin, Dongxue; Wang, Zhijian; Gao, Yingjie; Du, Yunfei; Organic & biomolecular chemistry 23 (2025) 8479–8486; doi:10.1039/d5ob01126d

data_7160702
_publ_section_title
;
 Oxidative rearrangement of indoles mediated by 2-bromoethanol and
 hydrogen peroxide to access spirooxindoles.
;
_journal_issue                   37
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8479
_journal_page_last               8486
_journal_paper_doi               10.1039/d5ob01126d
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C17 H22 N2 O4'
_chemical_formula_sum            'C17 H22 N2 O4'
_chemical_formula_weight         318.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-03 deposited with the CCDC.	2025-08-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.691(4)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.8864(7)
_cell_length_b                   5.8178(2)
_cell_length_c                   25.8026(10)
_cell_measurement_reflns_used    3481
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      73.8290
_cell_measurement_theta_min      3.5600
_cell_volume                     3147.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.933
_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     52.00  98.00   0.50    1.00    --  105.17 -94.00   0.00   92
  2  \w     71.00 104.00   0.50    1.00    --  105.17 -94.00  90.00   66
  3  \w     35.00  62.00   0.50    1.00    --  105.17 -94.00  90.00   54
  4  \w    -16.00  18.00   0.50    0.25    --   47.02 -10.00  97.00   68
  5  \w    -24.00  38.00   0.50    0.25    --   47.02 -37.00 -30.00  124
  6  \w     62.00  87.00   0.50    1.00    --  105.17 -94.00-180.00   50
  7  \w    119.00 174.00   0.50    1.00    --  105.17  15.00-180.00  110
  8  \w     83.00 150.00   0.50    1.00    --  105.17  10.00 -88.00  134
  9  \w     53.00 121.00   0.50    0.25    --   47.02  10.00 -88.00  136
 10  \w   -105.00 -27.00   0.50    1.00    -- -100.00  77.00  60.00  156
 11  \w   -107.00 -63.00   0.50    1.00    -- -100.00  77.00 -30.00   88
 12  \w    -60.00 -34.00   0.50    1.00    -- -100.00  77.00 -30.00   52
 13  \w    -72.00 -29.00   0.50    1.00    -- -100.00  61.00-180.00   86
 14  \w    -70.00 -45.00   0.50    1.00    -- -100.00  61.00-150.00   50
 15  \w    -54.00 -29.00   0.50    1.00    -- -100.00  45.00-150.00   50
 16  \w    -54.00 -28.00   0.50    1.00    -- -100.00  45.00-120.00   52
 17  \w    -23.00   2.00   0.50    0.25    --  -47.02  10.00 -88.00   50
 18  \w    -73.00 -38.00   0.50    1.00    -- -100.00  61.00 -30.00   70
 19  \w    -54.00 -27.00   0.50    1.00    -- -100.00  45.00 120.00   54
 20  \w   -152.00 -79.00   0.50    1.00    -- -100.00 -10.00  97.00  146
 21  \w   -115.00 -29.00   0.50    0.25    --  -47.02 -10.00  97.00  172
 22  \w    -77.00 -31.00   0.50    0.25    --  -47.02 125.00 -90.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0692019000
_diffrn_orient_matrix_UB_12      -0.0338289000
_diffrn_orient_matrix_UB_13      -0.0354338000
_diffrn_orient_matrix_UB_21      0.0231998000
_diffrn_orient_matrix_UB_22      -0.0035601000
_diffrn_orient_matrix_UB_23      -0.0509898000
_diffrn_orient_matrix_UB_31      0.0086005000
_diffrn_orient_matrix_UB_32      -0.2626449000
_diffrn_orient_matrix_UB_33      0.0052279000
_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  0.0449
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       2
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            9956
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.639
_diffrn_reflns_theta_min         3.577
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.789
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62752
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.141a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       needle
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     216
_refine_ls_number_reflns         3062
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0401
_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^)+(0.0509P)^2^+1.3682P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0949
_refine_ls_wR_factor_ref         0.1024
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2411
_reflns_number_total             3062
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01126d2.cif
_cod_data_source_block           xda_93_100k_1_auto
_cod_depositor_comments          'Adding full bibliography for 7160702.cif.'
_cod_database_code               7160702
_shelx_shelxl_version_number     2019/3
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C35(H35A,H35B), C27(H27A,H27B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C49(H49), C46(H46), C40(H40)
2.c Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C24(H24A,H24B,H24C), C34(H34A,H34B,H34C), C10(H10A,H10B,
 H10C)
;
_shelx_res_checksum              38718
_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 1.811
_oxdiff_exptl_absorpt_empirical_full_min 0.702