Selective Cu-Catalyzed Intramolecular Annulation of 3-Aryl/Heteryl-2-(diazoacetyl)-1<i>H</i>-pyrroles: Synthesis of Benzo/Furo/Thieno[<i>e</i>]-Fused 1<i>H</i>-Indol-7-oles and Their Transformations.
Bodunov, Vladimir A.; Galenko, Ekaterina E.; Sakharov, Pavel A.; Novikov, Mikhail S.; Khlebnikov, Alexander F.; The Journal of organic chemistry 84 (2019) 10388–10401; doi:10.1021/acs.joc.9b01573

data_4034060
_publ_section_title
;
 Selective Cu-Catalyzed Intramolecular Annulation of
 3-Aryl/Heteryl-2-(diazoacetyl)-1<i>H</i>-pyrroles: Synthesis of
 Benzo/Furo/Thieno[<i>e</i>]-Fused 1<i>H</i>-Indol-7-oles and Their
 Transformations.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10388
_journal_page_last               10401
_journal_paper_doi               10.1021/acs.joc.9b01573
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C30 H19 B F2 N2 O'
_chemical_formula_sum            'C30 H19 B F2 N2 O'
_chemical_formula_weight         472.28
_chemical_melting_point          341.0(10)
_chemical_name_common            'boron complex'
_chemical_name_systematic
(8,8-difluoro-6-phenyl-8H-8(lambda)4,9(lambda)4-benzo[e]pyrido[1&#x0092;,2&#x0092;:1,6][1,3,2]diazaborinino[5,4,3-hi]indol-5-yl)(phenyl)methanone
_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     dual
_audit_creation_date             2019-06-02
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90.750(2)
_cell_angle_beta                 90.793(2)
_cell_angle_gamma                101.350(2)
_cell_formula_units_Z            2
_cell_length_a                   7.16230(10)
_cell_length_b                   11.1474(2)
_cell_length_c                   14.1885(3)
_cell_measurement_reflns_used    10638
_cell_measurement_temperature    116.0(3)
_cell_measurement_theta_max      72.5450
_cell_measurement_theta_min      3.0950
_cell_volume                     1110.42(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      116.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -95.00 -56.00   0.50    0.20    --  -38.95 -36.00 -49.00   78
  2  \w    -32.00  14.00   0.50    0.20    --  -38.95  36.00 107.00   92
  3  \w    -51.00 -25.00   0.50    0.20    --  -38.95 -36.00 -49.00   52
  4  \w     57.00  96.00   0.50    0.20    --   38.95  36.00 107.00   78
  5  \w     95.00 151.00   0.50    0.56    --  104.92  36.00 107.00  112
  6  \w     39.00 120.00   0.50    0.56    --  104.92 -36.00 -49.00  162
  7  \w    -79.00 -12.00   0.50    0.20    --  -38.95 -77.00   0.00  134
  8  \w    -63.00   3.00   0.50    0.20    --  -38.95  77.00 -90.00  132
  9  \w   -105.00 -58.00   0.50    0.20    --  -38.95 -32.00 -90.00   94
 10  \w    -16.00  10.00   0.50    0.20    --   38.95 -43.00 150.00   52
 11  \w    -11.00  50.00   0.50    0.20    --   38.95 -43.00 120.00  122
 12  \w     70.00 108.00   0.50    0.20    --   38.95  32.00-120.00   76
 13  \w     24.00  49.00   0.50    0.20    --   38.95 -36.00 -49.00   50
 14  \w    -25.00   0.00   0.50    0.20    --   38.95 -54.00-150.00   50
 15  \w     25.00  53.00   0.50    0.20    --   38.95 -43.00 150.00   56
 16  \w     15.00  53.00   0.50    0.20    --   38.95 -54.00-150.00   76
 17  \w     42.00 127.00   0.50    0.56    --  104.92 -77.00-120.00  170
 18  \w     79.00 105.00   0.50    0.56    --  104.92 -30.00 120.00   52
 19  \w     71.00 117.00   0.50    0.56    --  104.92 -37.00 150.00   92
 20  \w     93.00 157.00   0.50    0.56    --  104.92  30.00 150.00  128
 21  \w     39.00 118.00   0.50    0.56    --  104.92 -77.00   0.00  158
 22  \w     90.00 145.00   0.50    0.56    --  104.92  37.00-180.00  110
 23  \w     86.00 111.00   0.50    0.56    --  104.92  22.00   0.00   50
 24  \w     82.00 127.00   0.50    0.56    --  104.92 -69.00 120.00   90
 25  \w    131.00 156.00   0.50    0.56    --  104.92  77.00 120.00   50
 26  \w     86.00 154.00   0.50    0.56    --  104.92 111.00  60.00  136
 27  \w     83.00 109.00   0.50    0.56    --  104.92  77.00 120.00   52
 28  \w     53.00 115.00   0.50    0.56    --  104.92 -53.00   0.00  124
 29  \w     62.00 141.00   0.50    0.56    --  104.92 178.00 -60.00  158
 30  \w     40.00  65.00   0.50    0.56    --  104.92 -69.00 120.00   50
 31  \w     74.00  99.00   0.50    0.56    --  104.92-111.00 -30.00   50
 32  \w    -37.00 -12.00   0.50    0.20    --  -38.95  36.00 107.00   50
 33  \w    -69.00 -19.00   0.50    0.20    --  -38.95 -65.00 150.00  100
 34  \w    -21.00  23.00   0.50    0.20    --  -38.95  77.00 120.00   88
 35  \w    -66.00 -31.00   0.50    0.20    --  -38.95  77.00 120.00   70
 36  \w    -24.00   2.00   0.50    0.20    --   38.95 -32.00-150.00   52
 37  \w     56.00  82.00   0.50    0.20    --   38.95  65.00-120.00   52
 38  \w     22.00  69.00   0.50    0.20    --   38.95  65.00-150.00   94
 39  \w     21.00  54.00   0.50    0.20    --   38.95  54.00-180.00   66
 40  \w     28.00  54.00   0.50    0.20    --   38.95  32.00-120.00   52
 41  \w     12.00  63.00   0.50    0.20    --   38.95  77.00-120.00  102
 42  \w     61.00  86.00   0.50    0.20    --   38.95  54.00-180.00   50
 43  \w     27.00  52.00   0.50    0.20    --   38.95  77.00-180.00   50
 44  \w     26.00  65.00   0.50    0.20    --   38.95  77.00 -60.00   78
 45  \w     81.00 106.00   0.50    0.20    --   38.95  77.00   0.00   50
 46  \w     29.00  54.00   0.50    0.20    --   38.95  65.00-120.00   50
 47  \w    117.00 156.00   0.50    0.56    --  104.92  77.00-180.00   78
 48  \w    132.00 157.00   0.50    0.56    --  104.92  53.00-150.00   50
 49  \w     87.00 113.00   0.50    0.56    --  104.92  53.00-150.00   52
 50  \w    119.00 145.00   0.50    0.56    --  104.92  53.00-180.00   52
 51  \w     83.00 114.00   0.50    0.56    --  104.92  61.00 -90.00   62
 52  \w     81.00 132.00   0.50    0.56    --  104.92  69.00-120.00  102
 53  \w     88.00 114.00   0.50    0.56    --  104.92  53.00-180.00   52
 54  \w     85.00 111.00   0.50    0.56    --  104.92  53.00 -90.00   52
 55  \w     85.00 110.00   0.50    0.56    --  104.92  61.00 150.00   50
 56  \w    132.00 157.00   0.50    0.56    --  104.92  37.00 -60.00   50
 57  \w     85.00 116.00   0.50    0.56    --  104.92  53.00-120.00   62
 58  \w     80.00 106.00   0.50    0.56    --  104.92  77.00-180.00   52
 59  \w    125.00 151.00   0.50    0.56    --  104.92  77.00 150.00   52
 60  \w     78.00 104.00   0.50    0.56    --  104.92  77.00-120.00   52
 61  \w     89.00 119.00   0.50    0.56    --  104.92 -37.00-120.00   60
 62  \w     92.00 118.00   0.50    0.56    --  104.92  37.00 150.00   52
 63  \w     74.00 101.00   0.50    0.56    --  104.92 -37.00  60.00   54
 64  \w     78.00 104.00   0.50    0.56    --  104.92  77.00 150.00   52
 65  \w     81.00 115.00   0.50    0.56    --  104.92  69.00 -90.00   68
 66  \w     83.00 110.00   0.50    0.56    --  104.92  61.00-150.00   54
 67  \w     81.00 106.00   0.50    0.56    --  104.92  69.00 150.00   50
 68  \w     42.00  68.00   0.50    0.56    --  104.92 -37.00  60.00   52
 69  \w     82.00 154.00   0.50    0.56    --  104.92  69.00-150.00  144
 70  \w     85.00 111.00   0.50    0.56    --  104.92  53.00 150.00   52
 71  \w     87.00 113.00   0.50    0.56    --  104.92  61.00-180.00   52
 72  \w     84.00 110.00   0.50    0.56    --  104.92  61.00-120.00   52
 73  \w     50.00  90.00   0.50    0.56    --  104.92 -69.00 -60.00   80
 74  \w     80.00 106.00   0.50    0.56    --  104.92  77.00-150.00   52
 75  \w     59.00  85.00   0.50    0.56    --  104.92 -37.00-120.00   52
 76  \w     81.00 107.00   0.50    0.56    --  104.92  69.00-180.00   52
 77  \w     13.00  39.00   0.50    0.20    --   38.95  77.00 150.00   52
 78  \w     28.00  69.00   0.50    0.20    --   38.95-104.00-180.00   82
 79  \w     48.00  96.00   0.50    0.20    --   38.95-138.00  60.00   96
 80  \w     43.00  69.00   0.50    0.20    --   38.95 -89.00 -90.00   52
 81  \w    -15.00  11.00   0.50    0.20    --   38.95 -89.00 -90.00   52
 82  \w     56.00  82.00   0.50    0.56    --  104.92 -86.00 150.00   52
 83  \w     94.00 134.00   0.50    0.56    --  104.92 -86.00 150.00   80
 84  \w     78.00 106.00   0.50    0.56    --  104.92-111.00  30.00   56
 85  \w    116.00 148.00   0.50    0.56    --  104.92  30.00  90.00   64
 86  \w    112.00 138.00   0.50    0.56    --  104.92  93.00  90.00   52
 87  \w     89.00 125.00   0.50    0.56    --  104.92-133.00 150.00   72
 88  \w     62.00 112.00   0.50    0.56    --  104.92-111.00 -60.00  100
 89  \w     40.00  67.00   0.50    0.56    --  104.92-111.00 -30.00   54
 90  \w     83.00 109.00   0.50    0.56    --  104.92  61.00-180.00   52
 91  \w    132.00 157.00   0.50    0.56    --  104.92  61.00-180.00   50
 92  \w     88.00 113.00   0.50    0.56    --  104.92-111.00 -90.00   50
 93  \w     49.00 114.00   0.50    0.56    --  104.92-111.00 150.00  130
 94  \w    -12.00  27.00   0.50    0.20    --   38.95 -37.00 -49.00   78
 95  \w    -36.00 -11.00   0.50    0.20    --    0.00 110.00 -55.54   50
 96  \w    -18.00   7.00   0.50    0.20    --   24.00 111.00 -45.62   50
 97  \w     -7.00  18.00   0.50    0.20    --   28.00  99.00 172.92   50
 98  \w     -7.00  18.00   0.50    0.20    --   28.00  98.00  73.93   50
 99  \w     -1.00  24.00   0.50    0.20    --   32.00  94.00  17.38   50
100  \w      1.00  26.00   0.50    0.20    --   32.00  88.00 -55.60   50
101  \w      4.00  29.00   0.50    0.20    --   36.00  90.00-176.65   50
102  \w     17.00  57.00   0.50    0.20    --   38.95 -65.00 -90.00   80
103  \w     26.00  68.00   0.50    0.20    --   38.95 -89.00  60.00   84
104  \w     11.00  36.00   0.50    0.20    --   40.00  84.00 132.76   50
105  \w     11.00  36.00   0.50    0.20    --   40.00  84.00 -12.68   50
106  \w     16.00  41.00   0.50    0.20    --   44.00  81.00-127.30   50
107  \w     16.00  41.00   0.50    0.20    --   44.00  80.00 168.24   50
108  \w     16.00  41.00   0.50    0.20    --   44.00  82.00  96.84   50
109  \w     16.00  41.00   0.50    0.20    --   44.00  81.00-109.50   50
110  \w     17.00  42.00   0.50    0.20    --   44.00  79.00 -19.99   50
111  \w     16.00  41.00   0.50    0.20    --   44.00  80.00  22.41   50
112  \w     16.00  41.00   0.50    0.20    --   44.00  81.00  48.23   50
113  \w     17.00  42.00   0.50    0.20    --   44.00  79.00 -73.20   50
114  \w     28.00  54.00   0.50    0.20    --   52.00  77.00-134.36   52
115  \w     29.00  54.00   0.50    0.20    --   56.00  77.00 -25.74   50
116  \w     30.00  56.00   0.50    0.20    --   56.00  74.00 167.26   52
117  \w     31.00  57.00   0.50    0.20    --   56.00  76.00  24.25   52
118  \w     37.00  62.00   0.50    0.20    --   64.00  77.00-173.84   50
119  \w     88.00 127.00   0.50    0.20    --   64.00  74.00  91.31   78
120  \w     38.00  72.00   0.50    0.20    --   64.00  74.00  91.31   68
121  \w     42.00  78.00   0.50    0.20    --   64.00  59.00  52.94   72
122  \w     37.00  63.00   0.50    0.20    --   64.00  77.00 121.62   52
123  \w     47.00  74.00   0.50    0.20    --   64.00  62.00 165.93   54
124  \w    104.00 129.00   0.50    0.20    --   64.00  59.00  52.94   50
125  \w     51.00  95.00   0.50    0.20    --   68.00  49.00-160.56   88
126  \w     43.00  85.00   0.50    0.20    --   68.00  74.00 -77.51   84
127  \w     81.00 107.00   0.50    0.20    --   68.00  72.00 -96.47   52
128  \w     43.00  68.00   0.50    0.20    --   68.00  72.00 -96.47   50
129  \w     48.00 134.00   0.50    0.20    --   68.00  66.00 139.34  172
130  \w     50.00  76.00   0.50    0.20    --   72.00  69.00-124.90   52
131  \w     48.00  74.00   0.50    0.20    --   72.00  73.00  62.24   52
132  \w     48.00  94.00   0.50    0.20    --   72.00  69.00 -14.39   92
133  \w     49.00  77.00   0.50    0.56    --   76.00  77.00-157.29   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1995908000
_diffrn_orient_matrix_UB_12      0.0404051000
_diffrn_orient_matrix_UB_13      0.0453115000
_diffrn_orient_matrix_UB_21      0.0025899000
_diffrn_orient_matrix_UB_22      -0.1338785000
_diffrn_orient_matrix_UB_23      0.0245602000
_diffrn_orient_matrix_UB_31      0.0910969000
_diffrn_orient_matrix_UB_32      -0.0178267000
_diffrn_orient_matrix_UB_33      -0.0955939000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0217
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            17717
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.483
_diffrn_reflns_theta_min         3.115
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.792
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.413
_exptl_crystal_description       plate
_exptl_crystal_F_000             488
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.212
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.042
_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     325
_refine_ls_number_reflns         4375
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0542P)^2^+0.2598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0960
_refine_ls_wR_factor_ref         0.0989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3952
_reflns_number_total             4375
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b01573_si_003.cif
_cod_data_source_block           1
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '340-342' was changed to
'341.0(10)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 6909 2019-04-08 15:41:33Z antanas 
;
_cod_database_code               4034060
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'F2 B N2 C19'
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C14(H14), C8(H8), C5(H5), C6(H6), C17(H17), C7(H7), C15(H15),
 C16(H16), C26(H26), C24(H24), C30(H30), C20(H20), C27(H27), C23(H23), C21(H21),
  C29(H29), C28(H28), C22(H22)
;
_shelx_res_checksum              97012
_shelx_hkl_checksum              42719
_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 1.225
_oxdiff_exptl_absorpt_empirical_full_min 0.875