Dearomatizative aminoetherification and diamination of indoles enabled by photochemical nitrene transfer reactions
Zhang, Li-Hua; Xie, Yang; Xuan, Jun; Chemical Communications 61 (2025) 8528–8531; doi:10.1039/D5CC02416A

data_7134522
_publ_section_title
;
 Dearomatizative aminoetherification and diamination of indoles enabled by
 photochemical nitrene transfer reactions
;
_journal_issue                   47
_journal_name_full               'Chemical Communications'
_journal_page_first              8528
_journal_page_last               8531
_journal_paper_doi               10.1039/D5CC02416A
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C22 H28 N2 O5 S'
_chemical_formula_sum            'C22 H28 N2 O5 S'
_chemical_formula_weight         432.52
_chemical_name_systematic        1
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2024-08-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-12-04 deposited with the CCDC.	2025-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                84.709(2)
_cell_angle_beta                 76.197(3)
_cell_angle_gamma                89.722(2)
_cell_formula_units_Z            2
_cell_length_a                   10.0397(3)
_cell_length_b                   10.2947(2)
_cell_length_c                   11.3136(4)
_cell_measurement_reflns_used    5867
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      67.6630
_cell_measurement_theta_min      4.0190
_cell_volume                     1130.54(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.960
_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     62.00 124.00   0.50    0.50    --   42.30  65.00-180.00  124
  2  \w    105.00 130.00   0.50    0.50    --   42.30  11.00  90.00   50
  3  \w    -43.00  10.00   0.50    0.50    --   42.30 -65.00 150.00  106
  4  \w     19.00  69.00   0.50    0.50    --   42.30 -82.00-150.00  100
  5  \w     25.00  65.00   0.50    0.50    --   42.30 -65.00 -30.00   80
  6  \w     37.00  69.00   0.50    0.50    --   42.30 -82.00 -60.00   64
  7  \w     25.00  63.00   0.50    0.50    --   42.30 -77.00 120.00   76
  8  \w     28.00  57.00   0.50    0.50    --   42.30 -65.00 150.00   58
  9  \w    -47.00 -21.00   0.50    0.50    --   42.30 -82.00 -60.00   52
 10  \w     50.00  79.00   0.50    0.50    --   42.30  11.00  90.00   58
 11  \w     18.00  57.00   0.50    0.50    --   42.30  65.00-180.00   78
 12  \w    -39.00  -4.00   0.50    0.50    --   42.30  11.00  90.00   70
 13  \w    -47.00  18.00   0.50    0.50    --   42.30 -65.00 -30.00  130
 14  \w     13.00  68.00   0.50    0.50    --   42.30 -82.00  54.56  110
 15  \w    -40.00 -15.00   0.50    0.50    --   42.30 -82.00  54.56   50
 16  \w    -44.00  12.00   0.50    0.50    --   42.30 -82.00 -90.00  112
 17  \w     23.00  61.00   0.50    0.50    --   42.30 -82.00 -90.00   76
 18  \w    -38.00  15.00   0.50    0.50    --   42.30 -77.00 120.00  106
 19  \w      7.00 121.00   0.50    0.59    --   93.40 -59.00 150.00  228
 20  \w     49.00 109.00   0.50    0.59    --   93.40 -82.00-150.00  120
 21  \w      5.00  62.00   0.50    0.59    --   93.40 -82.00 -30.00  114
 22  \w      5.00  83.00   0.50    0.59    --   93.40 -77.00 -90.00  156
 23  \w     51.00 104.00   0.50    0.59    --   93.40 -82.00 -60.00  106
 24  \w      4.00 183.00   0.50    0.59    --   93.40   0.00 -30.00  358
 25  \w     14.00 102.00   0.50    0.59    --   93.40 -82.00 150.00  176
 26  \w     57.00 105.00   0.50    0.59    --   93.40 -82.00  30.00   96
 27  \w     10.00 113.00   0.50    0.59    --   93.40 -33.00 -30.00  206
 28  \w      9.00  57.00   0.50    0.59    --   93.40 -82.00  90.00   96
 29  \w     75.00 102.00   0.50    0.59    --   93.40 -82.00  90.00   54
 30  \w     59.00  87.00   0.50    0.59    --   93.40  33.00-180.00   56
 31  \w     65.00  90.00   0.50    0.59    --   93.40 -82.00-120.00   50
 32  \w    106.00 132.00   0.50    0.59    --   93.40  68.00-150.00   52
 33  \w    103.00 128.00   0.50    0.59    --   93.40 -33.00 150.00   50
 34  \w      9.00  40.00   0.50    0.59    --   93.40 -68.00 -60.00   62
 35  \w     18.00  88.00   0.50    0.59    --   93.40 -33.00 150.00  140
 36  \w    157.00 182.00   0.50    0.59    --   93.40  33.00-180.00   50
 37  \w    113.00 139.00   0.50    0.59    --   93.40  33.00-180.00   52
 38  \w     10.00  83.00   0.50    0.59    --   93.40 -82.00 120.00  146
 39  \w      8.00 115.00   0.50    0.59    --   93.40 -59.00 -30.00  214
 40  \w     83.00 109.00   0.50    0.59    --   93.40 -82.00 -30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro II 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      0.1507167000
_diffrn_orient_matrix_UB_12      -0.0413859000
_diffrn_orient_matrix_UB_13      -0.0380943000
_diffrn_orient_matrix_UB_21      0.0063373000
_diffrn_orient_matrix_UB_22      0.0538005000
_diffrn_orient_matrix_UB_23      -0.1329209000
_diffrn_orient_matrix_UB_31      0.0471080000
_diffrn_orient_matrix_UB_32      0.1341121000
_diffrn_orient_matrix_UB_33      0.0267661000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_unetI/netI     0.0342
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            9666
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.899
_diffrn_reflns_theta_min         4.041
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.562
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.47085
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             460
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.420
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         3941
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0499
_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^)+(0.0859P)^2^+0.1925P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1418
_refine_ls_wR_factor_ref         0.1459
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3476
_reflns_number_total             3941
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc02416a2.cif
_cod_data_source_block           1111_auto
_cod_depositor_comments          'Adding full bibliography for 7134522.cif.'
_cod_database_code               7134522
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.926
_shelx_estimated_absorpt_t_min   0.885
_diffrn_oxdiff_digest_frames
;
01df1b47bbf854fbd631b02ee49b20709700029fac3
;
_diffrn_oxdiff_digest_hkl
;
0170ee0f39e74ebf203498574d4da882d64fa3
;
_reflns_odcompleteness_completeness 97.00
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: C1(0.75) H1A(0.75) H1B(0.75) H1C(0.75) C2(0.75) H2A(0.75)
 H2B(0.75) H2C(0.75) C3(0.75) H3A(0.75) H3B(0.75) H3C(0.75) C2A(0.25)
 H2AA(0.25) H2AB(0.25) H2AC(0.25) C1A(0.25) H1AA(0.25) H1AB(0.25) H1AC(0.25)
 C3A(0.25) H3AA(0.25) H3AB(0.25) H3AC(0.25)
3.a Ternary CH refined with riding coordinates:
 C8(H8), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B)
3.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C20(H20),
 C21(H21)
3.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C22(H22A,H22B,H22C), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C),
 C3(H3A,H3B,H3C), C2A(H2AA,H2AB,H2AC), C1A(H1AA,H1AB,H1AC), C3A(H3AA,H3AB,H3AC)
;
_shelx_res_checksum              27197
_shelx_hkl_checksum              48015
_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 2.968
_oxdiff_exptl_absorpt_empirical_full_min 0.548