Construction of the Pyrrolo[2,3-<i>d</i>]carbazole Core of Spiroindoline Alkaloids by Gold-Catalyzed Cascade Cyclization of Ynamide.
Matsuoka, Junpei; Kumagai, Hiroshi; Inuki, Shinsuke; Oishi, Shinya; Ohno, Hiroaki; The Journal of organic chemistry 84 (2019) 9358–9363; doi:10.1021/acs.joc.9b01149

data_4034160
_publ_section_title
;
 Construction of the Pyrrolo[2,3-<i>d</i>]carbazole Core of Spiroindoline
 Alkaloids by Gold-Catalyzed Cascade Cyclization of Ynamide.
;
_journal_issue                   14
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              9358
_journal_page_last               9363
_journal_paper_doi               10.1021/acs.joc.9b01149
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C34 H38 N4 O3 S'
_chemical_formula_sum            'C34 H38 N4 O3 S'
_chemical_formula_weight         582.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_audit_update_record
;
2019-04-20 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 102.9690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.12450(10)
_cell_length_b                   23.37440(10)
_cell_length_c                   14.44580(10)
_cell_measurement_reflns_used    63422
_cell_measurement_temperature    93
_cell_measurement_theta_max      73.1630
_cell_measurement_theta_min      1.9080
_cell_volume                     3002.40(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_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_temperature      93
_diffrn_detector                 'PLATUS 200K area detector'
_diffrn_detector_area_resol_mean 5.811
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.976
_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     60.00  86.00   0.50    0.50    --    5.00  60.00 150.00   52
  2  \w     46.00  72.00   0.50    0.50    --    5.00  50.00  90.00   52
  3  \w   -134.00 -44.00   0.50    0.50    --  -45.20  60.00  60.00  180
  4  \w    -77.00 -15.00   0.50    0.50    --  -45.20  10.00   0.00  124
  5  \w     14.00  43.00   0.50    0.50    --  -45.20  10.00   0.00   58
  6  \w   -104.00 -39.00   0.50    0.50    --  -45.20  60.00 150.00  130
  7  \w   -126.00-101.00   0.50    0.50    --  -45.20  10.00   0.00   50
  8  \w    -57.00 -24.00   0.50    0.50    -- -101.50  10.00 120.00   66
  9  \w   -189.00 -75.00   0.50    0.50    -- -101.50  10.00 120.00  228
 10  \w    -67.00 -41.00   0.50    0.50    -- -101.50  60.00  -1.07   52
 11  \w    -54.00 -28.00   0.50    0.50    -- -101.50  50.00  90.00   52
 12  \w   -189.00 -84.00   0.50    0.50    -- -101.50  50.00  90.00  210
 13  \w   -188.00 -88.00   0.50    0.50    -- -101.50  60.00 177.96  200
 14  \w   -183.00-156.00   0.50    0.50    -- -101.50  60.00 131.13   54
 15  \w   -163.00 -28.00   0.50    0.50    -- -101.50  51.00 156.68  270
 16  \w   -114.00 -88.00   0.50    0.50    -- -101.50  60.00  -1.07   52
 17  \w    -65.00 -40.00   0.50    0.50    -- -101.50  60.00 131.13   50
 18  \w   -148.00-104.00   0.50    0.50    -- -101.50  60.00  48.14   88
 19  \w   -174.00-133.00   0.50    0.50    -- -101.50  60.00  -1.07   82
 20  \w     11.00  40.00   0.50    0.50    --    5.00  20.00  60.00   58
 21  \w     58.00  84.00   0.50    0.50    --    5.00  20.00  60.00   52
 22  \w     60.00  89.00   0.50    0.50    --    5.00  50.00  30.00   58
 23  \w    -70.00 -34.00   0.50    0.50    --    5.00  40.00 120.00   72
 24  \w    -78.00 -18.00   0.50    0.50    --  -45.20  39.00 179.59  120
 25  \w     -5.00  44.00   0.50    0.50    --  -45.20  39.00 179.59   98
 26  \w   -135.00 -80.00   0.50    0.50    --  -45.20  60.00   0.00  110
 27  \w   -125.00 -95.00   0.50    0.50    --  -45.20  39.00 179.59   60
 28  \w   -128.00-103.00   0.50    0.50    --  -45.20  60.00 150.00   50
 29  \w   -113.00 -60.00   0.50    0.50    -- -101.50  60.00 134.52  106
 30  \w   -190.00-164.00   0.50    0.50    -- -101.50   9.00  -6.77   52
 31  \w   -169.00-144.00   0.50    0.50    -- -101.50  60.00 134.52   50
 32  \w    -97.00 -70.00   0.50    0.50    -- -101.50  15.00  -8.15   54
 33  \w   -189.00-118.00   0.50    0.50    -- -101.50   0.00   0.00  142
 34  \w   -100.00 -74.00   0.50    0.50    -- -101.50  50.00   0.00   52
 35  \w   -190.00-112.00   0.50    0.50    -- -101.50  50.00   0.00  156
 36  \w    -38.00 -13.00   0.50    0.50    -- -101.50   5.00  -9.00   50
 37  \w   -190.00-149.00   0.50    0.50    -- -101.50  40.00   0.00   82
 38  \w    -74.00 -38.00   0.50    0.50    -- -101.50  60.00  85.63   72
 39  \w   -120.00 -94.00   0.50    0.50    -- -101.50  60.00  85.63   52
 40  \w   -189.00-137.00   0.50    0.50    -- -101.50  60.00  85.63  104
 41  \w    -43.00 -14.00   0.50    0.50    -- -101.50   0.00 150.00   58
 42  \w   -190.00-164.00   0.50    0.50    -- -101.50   5.00  -9.00   52
 43  \w   -190.00-112.00   0.50    0.50    -- -101.50  15.00  -8.15  156
 44  \w   -113.00 -37.00   0.50    0.50    -- -101.50  47.00 176.44  152
 45  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00 150.00  116
 46  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00 120.00   92
 47  \w     38.00  94.00   0.50    0.50    --    5.00  60.00  60.00  112
 48  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00  90.00   92
 49  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00  60.00  358
 50  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00  90.00  358
 51  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00   0.00  358
 52  \w   -135.00  44.00   0.50    0.50    --  -45.20  39.00 169.46  358
 53  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00   0.00  358
 54  \w   -135.00 -88.00   0.50    0.50    --  -45.20   5.00  -8.41   94
 55  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00 120.00  358
 56  \w    -84.00  94.00   0.50    0.50    --    5.00  20.00  90.00  356
 57  \w    -84.00  94.00   0.50    0.50    --    5.00  40.00 150.00  356
 58  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00   0.00   92
 59  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00  30.00   92
 60  \w    -84.00  94.00   0.50    0.50    --    5.00  20.00  30.00  356
 61  \w    -84.00  94.00   0.50    0.50    --    5.00  40.00  30.00  356
 62  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00 120.00  116
 63  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00  60.00   92
 64  \w     38.00  94.00   0.50    0.50    --    5.00  60.00  90.00  112
 65  \w    -84.00 -26.00   0.50    0.50    --    5.00  50.00  90.00  116
 66  \w    -84.00  94.00   0.50    0.50    --    5.00  30.00 150.00  356
 67  \w    -84.00  94.00   0.50    0.50    --    5.00  30.00 120.00  356
 68  \w   -135.00  44.00   0.50    0.50    --  -45.20  10.00 150.00  358
 69  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00 150.00  358
 70  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00 150.00  358
 71  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00 120.00  358
 72  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00  90.00  358
 73  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00  60.00  358
 74  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00  30.00  358
 75  \w   -135.00  44.00   0.50    0.50    --  -45.20   0.00   0.00  358
 76  \w   -135.00  44.00   0.50    0.50    --  -45.20  20.00   0.00  358
 77  \w   -135.00  44.00   0.50    0.50    --  -45.20  40.00  30.00  358
 78  \w   -190.00 -13.00   0.50    0.50    -- -101.50  40.00 120.00  354
 79  \w   -190.00 -13.00   0.50    0.50    -- -101.50  40.00   0.00  354
 80  \w   -190.00 -13.00   0.50    0.50    -- -101.50  40.00  30.00  354
 81  \w   -190.00-139.00   0.50    0.50    -- -101.50  40.00  90.00  102
 82  \w   -190.00 -13.00   0.50    0.50    -- -101.50   0.00  60.00  354
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0442355000
_diffrn_orient_matrix_UB_12      -0.0446466000
_diffrn_orient_matrix_UB_13      -0.0672849000
_diffrn_orient_matrix_UB_21      -0.0370262000
_diffrn_orient_matrix_UB_22      -0.0484526000
_diffrn_orient_matrix_UB_23      0.0633229000
_diffrn_orient_matrix_UB_31      -0.1634402000
_diffrn_orient_matrix_UB_32      -0.0011369000
_diffrn_orient_matrix_UB_33      -0.0586119000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0449
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            110139
_diffrn_reflns_point_group_measured_fraction_full 0.956
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.694
_diffrn_reflns_theta_min         3.139
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              micromax007
_exptl_absorpt_coefficient_mu    1.286
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.289
_exptl_crystal_description       block
_exptl_crystal_F_000             1240
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.554
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 4832 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.004(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     761
_refine_ls_number_reflns         11284
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0409
_refine_ls_R_factor_gt           0.0398
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0602P)^2^+1.2588P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1042
_refine_ls_wR_factor_ref         0.1048
_reflns_Friedel_coverage         0.860
_reflns_Friedel_fraction_full    0.920
_reflns_Friedel_fraction_max     0.883
_reflns_number_gt                10936
_reflns_number_total             11284
_reflns_threshold_expression     'I > 2\s(I)'
_publcif_datablock.id            {f6b3187a-948e-401f-bc39-3b903742d3f0}
_publcif_info_exptl_table_max_cols 4
_publcif_info_exptl_table_use_headnotes n
_cod_data_source_file            jo9b01149_si_002.cif
_cod_data_source_block           vindrosin_190305
_cod_database_code               4034160
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C34 H38 N4 O3 S1'
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.882
_reflns_odcompleteness_completeness 99.04
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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 Ternary CH refined with riding coordinates:
 C00H(H00H), C00W(H00W), C016(H016), C01A(H01Q)
2.b Secondary CH2 refined with riding coordinates:
 C00S(H00A,H00B), C013(H01A,H01B), C019(H01C,H01D), C01C(H01E,H01F), C01F(H01H,
 H01I), C01K(H01L,H01M), C01R(H01Y,H), C01S(H01O,H01P), C01V(H01,HA), C01Y(H2AA,
 HB), C022(H02I,H02J), C023(H02K,H02L), C027(H02G,H02H), C029(H02M,H02N),
 C02A(H02O,H02P), C02B(H02Q,H02R)
2.c Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00L(H00L), C00O(H00O), C00P(H00P), C00R(H00R), C00T(H00T),
 C00V(H00V), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C017(H017), C01E(H01G),
 C01G(H01R), C01H(H01J), C01I(H01S), C01J(H01K), C01L(H01T), C01M(H01V),
 C01N(H01N), C01O(H01W), C01P(H01X), C01T(H01Z), C01U(H01U), C01W(H0AA),
 C01X(H1AA), C020(H020), C026(H026), C028(H028)
2.d Idealised Me refined as rotating group:
 C01Z(H3AA,HC,HD), C024(H02A,H02B,H02C), C025(H02D,H02E,H02F), C02C(H02S,H02T,
 H02U)
;
_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 1.304
_oxdiff_exptl_absorpt_empirical_full_min 0.617