C-H functionalization of 2-alkyl tryptamines: direct assembly of azepino[4,5-<i>b</i>]indoles and total synthesis of ngouniensines.
Xie, Kejing; Shen, Zeyuan; Cheng, Peng; Dong, Haoxiang; Yu, Zhi-Xiang; Zu, Liansuo; Chemical science 15 (2024) 12732–12738; doi:10.1039/d4sc02802c

data_1572102
_publ_section_title
;
 C-H functionalization of 2-alkyl tryptamines: direct assembly of
 azepino[4,5-<i>b</i>]indoles and total synthesis of ngouniensines.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              12732
_journal_page_last               12738
_journal_paper_doi               10.1039/d4sc02802c
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C29 H27 Br N2 O3'
_chemical_formula_sum            'C29 H27 Br N2 O3'
_chemical_formula_weight         531.43
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-10-14
_audit_creation_method
;
  Olex2 1.1
  (compiled 2011.02.15 svn.r1672, GUI svn.r3494)
;
_audit_update_record
;
2023-07-26 deposited with the CCDC.	2024-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                85.389(6)
_cell_angle_beta                 79.331(9)
_cell_angle_gamma                68.354(8)
_cell_formula_units_Z            1
_cell_length_a                   7.1378(8)
_cell_length_b                   8.1657(5)
_cell_length_c                   11.6045(11)
_cell_measurement_reflns_used    3830
_cell_measurement_temperature    116.5(3)
_cell_measurement_theta_max      71.0150
_cell_measurement_theta_min      3.8750
_cell_volume                     617.75(11)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution
'A short history of SHELX (Sheldrick, 2007)/Bruker'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      116.5(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0971
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.9991
_diffrn_measured_fraction_theta_max 0.8701
_diffrn_measurement_details
;
  1 omega  121.00  147.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

  2 omega  104.00  133.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   47.0000   78.3566 29

  3 omega   90.00  157.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 67

  4 omega  139.00  172.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 33

  5 omega  132.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 38

  6 omega  126.00  170.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 44

  7 omega   91.00  139.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   75.0000 -124.6720 48

  8 omega   94.00  154.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 60

  9 omega  121.00  148.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       80.0000   48.0000  -19.2610 27

 10 omega   88.00  131.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000 -150.0000 43

 11 omega   87.00  113.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -60.0000 26

 12 omega   81.00  155.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 74

 13 omega   82.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 25

 14 omega   81.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 26

 15 omega   84.00  110.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 26

 16 omega   81.00  175.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 94

 17 omega   78.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017   57.0000 -180.0000 25

 18 omega   76.00  113.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   79.0000 -157.7796 37

 19 omega   76.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   79.0000  -98.0035 26

 20 omega   63.00  101.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       80.0000   48.0000  -19.2610 38

 21 omega   81.00  149.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 68

 22 omega   91.00  164.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 73

 23 omega   90.00  171.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 81

 24 omega   82.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 25

 25 omega   81.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 26 omega   81.00  168.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 87

 27 omega   76.00  102.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  178.0000 -120.0000 26

 28 omega   68.00  108.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  178.0000  -30.0000 40

 29 omega   81.00  128.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -150.0000 47

 30 omega   82.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -180.0000 25

 31 omega   46.00   88.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   75.0000 -124.6720 42

 32 omega   24.00   50.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000 -147.4185 26

 33 omega   24.00   63.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   79.0000  -98.0035 39

 34 omega   24.00   49.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  -24.5644 25

 35 omega   64.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017   57.0000   30.0000 39

 36 omega   59.00  101.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -       76.0000   47.0000   78.3566 42

 37 omega   70.00  118.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   79.0000  134.1826 48

 38 omega   81.00  107.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  150.0000 26

 39 omega   31.00   72.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   79.0000   21.1459 41

 40 omega   25.00   52.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017   57.0000   30.0000 27

 41 omega   18.00   43.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   82.0000   80.6445 25

 42 omega   18.00   43.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   82.0000  102.7160 25

 43 omega   27.00   68.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   79.0000  134.1826 41

 44 omega   24.00   49.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  145.0089 25

 45 omega   10.00   35.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   90.0000  174.9877 25

 46 omega   39.00   68.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   40.0000  172.5514 29

 47 omega   47.00  122.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000  -90.0000 75

 48 omega   64.00  135.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000    0.0000 71

 49 omega   84.00  109.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  120.0000 25

 50 omega   41.00   75.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -99.0000   30.0000 34

 51 omega   53.00  104.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017 -178.0000   60.0000 51

 52 omega   39.00  116.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 77

 53 omega   47.00   75.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -99.0000 -180.0000 28

 54 omega   23.00   53.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -57.0000 -120.0000 30

 55 omega   -3.00   23.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -99.0000 -180.0000 26

 56 omega  -31.00   -3.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -57.0000 -120.0000 28

 57 omega  -10.00   34.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017  -57.0000    0.0000 44

 58 omega   41.00   95.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  150.0000 54

 59 omega   12.00   37.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   87.0000   21.7725 25

 60 omega    3.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   95.0000   52.5622 25

 61 omega    3.00   28.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   95.0000   73.6372 25

 62 omega  -18.00   25.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   40.0000  172.5514 43

 63 omega    4.00   29.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   94.0000  -44.5796 25

 64 omega   17.00   42.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   84.0000  -44.1874 25

 65 omega   20.00   47.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017   57.0000  -60.0000 27

 66 omega   20.00   63.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   79.0000 -157.7796 43

 67 omega   20.00   45.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       35.8017   57.0000 -180.0000 25

 68 omega   51.00  102.00   1.0000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1052976000
_diffrn_orient_matrix_UB_12      0.2010240000
_diffrn_orient_matrix_UB_13      0.0140305000
_diffrn_orient_matrix_UB_21      0.1059645000
_diffrn_orient_matrix_UB_22      0.0277764000
_diffrn_orient_matrix_UB_23      -0.1242559000
_diffrn_orient_matrix_UB_31      -0.1821280000
_diffrn_orient_matrix_UB_32      -0.0052056000
_diffrn_orient_matrix_UB_33      -0.0511489000
_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  0.0405
_diffrn_reflns_av_unetI/netI     0.0530
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8110
_diffrn_reflns_point_group_measured_fraction_full 0.894
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.107
_diffrn_reflns_theta_min         3.877
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.539
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.429
_exptl_crystal_F_000             274
_exptl_crystal_size_max          0.350
_exptl_crystal_size_mid          0.060
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.543
_refine_diff_density_min         -0.285
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 1606 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.017(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         4161
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0390
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0405P)^2^+0.1794P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.771
_reflns_Friedel_fraction_full    0.790
_reflns_Friedel_fraction_max     0.757
_reflns_number_gt                3970
_reflns_number_total             4161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02802c2.cif
_cod_data_source_block           exp_8216
_cod_depositor_comments
'Adding full bibliography for 1572101--1572103.cif.'
_cod_database_code               1572102
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelx_estimated_absorpt_t_max   0.963
_shelx_estimated_absorpt_t_min   0.470
_shelx_hkl_checksum              42142
_shelx_res_checksum              95424
_shelx_shelxl_version_number     2014/7