Iron(III)-catalyzed tandem annulation of indolyl-substituted <i>p</i>-quinone methides with ynamides for the synthesis of cyclopenta[<i>b</i>]indoles.
Yu, Ke-Yin; Ge, Xiao-Min; Fan, Yi-Jun; Liu, Xiao-Tao; Yang, Xue; Yang, Yu-Han; Zhao, Xian-He; An, Xian-Tao; Fan, Chun-An; Chemical communications (Cambridge, England) 58 (2022) 8710–8713; doi:10.1039/d2cc03252j

data_7130465
_publ_section_title
;
 Iron(III)-catalyzed tandem annulation of indolyl-substituted
 <i>p</i>-quinone methides with ynamides for the synthesis of
 cyclopenta[<i>b</i>]indoles.
;
_journal_issue                   62
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8710
_journal_page_last               8713
_journal_paper_doi               10.1039/d2cc03252j
_journal_volume                  58
_journal_year                    2022
_chemical_formula_moiety         'C46 H47 Br N2 O4 S'
_chemical_formula_sum            'C46 H47 Br N2 O4 S'
_chemical_formula_weight         803.82
_chemical_melting_point          478.6(5)
_chemical_name_systematic        'Compound 3ia'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-11-01
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-02-15 deposited with the CCDC.	2022-07-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.1700(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.55960(10)
_cell_length_b                   12.86910(10)
_cell_length_c                   30.3703(3)
_cell_measurement_reflns_used    18218
_cell_measurement_temperature    303.78(10)
_cell_measurement_theta_max      76.2650
_cell_measurement_theta_min      2.9020
_cell_volume                     4103.19(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      303.78(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.958
_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     92.00 176.00   0.50    0.05    --  104.25  45.00-150.00  168
  2  \w    106.00 176.00   0.50    0.05    --  104.25 104.00-120.00  140
  3  \w    -28.00  27.00   0.50    0.05    --   46.32 -19.00  60.00  110
  4  \w     35.00  61.00   0.50    0.05    --   46.32-104.00 137.00   52
  5  \w     75.00 105.00   0.50    0.05    --  104.25-104.00 137.00   60
  6  \w     34.00  83.00   0.50    0.05    --  104.25 -94.00-180.00   98
  7  \w     39.00  66.00   0.50    0.05    --  104.25 -61.00 -60.00   54
  8  \w     34.00  66.00   0.50    0.05    --  104.25 -61.00 -30.00   64
  9  \w     35.00  60.00   0.50    0.05    --  104.25 -61.00   0.00   50
 10  \w     35.00  71.00   0.50    0.05    --  104.25 -61.00  30.00   72
 11  \w     34.00  60.00   0.50    0.05    --  104.25 -61.00 120.00   52
 12  \w     35.00  60.00   0.50    0.05    --  104.25 -61.00 150.00   50
 13  \w   -104.00 -29.00   0.50    0.05    -- -102.00  77.00-120.00  150
 14  \w    -69.00 -30.00   0.50    0.05    -- -102.00  61.00  90.00   78
 15  \w    -66.00 -30.00   0.50    0.05    -- -102.00  61.00  60.00   72
 16  \w    -57.00 -29.00   0.50    0.05    -- -102.00  61.00  30.00   56
 17  \w    -58.00 -32.00   0.50    0.05    -- -102.00  61.00   0.00   52
 18  \w    -57.00 -32.00   0.50    0.05    -- -102.00  61.00 -30.00   50
 19  \w    -40.00  18.00   0.50    0.05    --  -46.32  37.00   0.00  116
 20  \w   -118.00 -76.00   0.50    0.05    --  -46.32-125.00 -60.00   84
 21  \w   -118.00 -84.00   0.50    0.05    --  -46.32-125.00 -90.00   68
 22  \w   -116.00 -90.00   0.50    0.05    --  -46.32-125.00-180.00   52
 23  \w    -81.00   1.00   0.50    0.05    --  -46.32 104.00-120.00  164
 24  \w   -105.00 -52.00   0.50    0.05    -- -102.00 104.00-120.00  106
 25  \w   -155.00 -86.00   0.50    0.05    -- -102.00-104.00 137.00  138
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0137903000
_diffrn_orient_matrix_UB_12      -0.1140250000
_diffrn_orient_matrix_UB_13      -0.0152422000
_diffrn_orient_matrix_UB_21      0.1442097000
_diffrn_orient_matrix_UB_22      -0.0162304000
_diffrn_orient_matrix_UB_23      0.0117463000
_diffrn_orient_matrix_UB_31      -0.0232784000
_diffrn_orient_matrix_UB_32      -0.0327051000
_diffrn_orient_matrix_UB_33      0.0472514000
_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  0.0556
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            29600
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.451
_diffrn_reflns_theta_min         2.927
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.193
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61496
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
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    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             1680
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane and methanol'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.329
_refine_diff_density_min         -0.755
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     497
_refine_ls_number_reflns         8255
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0629P)^2^+1.3607P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1316
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6899
_reflns_number_total             8255
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc03252j2.cif
_cod_data_source_block           Compound_3ia
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_melting_point' value '478.15-479.15' was changed
to '478.6(5)' -- the average value was taken and precision was
estimated.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_database_code               7130465
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Restrained distances
 H26C-H4
 2.1 with sigma of 0.01
 H4-H25A
 2.1 with sigma of 0.01
2.a Ternary CH refined with riding coordinates:
 C12(H12)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C14(H14), C18(H18), C28(H28), C29(H29), C30(H30),
 C31(H31), C32(H32), C34(H34), C35(H35), C36(H36), C37(H37), C41(H41), C42(H42),
  C44(H44), C45(H45)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C39(H39A,
 H39B,H39C), C46(H46A,H46B,H46C)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_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 4.755
_oxdiff_exptl_absorpt_empirical_full_min 0.385