C2/C4 Regioselective Heteroarylation of Indoles by Tuning C‒H Metalation Modes
Chen, Shuyou; Zhang, Min; Su, Rongchuan; Chen, Xingyu; Feng, Boya; Yang, Yudong; You, Jingsong; ACS Catalysis 9 (2019) 6372–; doi:10.1021/acscatal.9b01273

data_4514794
_publ_section_title
;
 C2/C4 Regioselective Heteroarylation of Indoles by Tuning C--H Metalation
 Modes
;
_journal_issue                   7
_journal_name_full               'ACS Catalysis'
_journal_page_first              6372
_journal_paper_doi               10.1021/acscatal.9b01273
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C32 H36 Ir N O2'
_chemical_formula_sum            'C32 H36 Ir N O2'
_chemical_formula_weight         658.82
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                76.588(3)
_cell_angle_beta                 87.879(2)
_cell_angle_gamma                89.094(3)
_cell_formula_units_Z            4
_cell_length_a                   11.5179(3)
_cell_length_b                   13.5428(6)
_cell_length_c                   18.4830(6)
_cell_measurement_reflns_used    8473
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.9470
_cell_measurement_theta_min      3.0780
_cell_volume                     2802.44(17)
_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    '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      293.15
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0874
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
  1 omega  -42.00   53.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9669   77.0000 -120.0000 95

  2 omega  -25.00   24.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9669  -99.0000    0.0000 49

  3 omega  -87.00  -32.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9669  178.0000 -150.0000 55

  4 omega  -26.00   50.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9669   38.0000   30.0000 76

  5 omega  -82.00   12.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      -14.9669  -77.0000  120.0000 94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0577631000
_diffrn_orient_matrix_UB_12      0.0137529000
_diffrn_orient_matrix_UB_13      -0.0103827000
_diffrn_orient_matrix_UB_21      0.0072254000
_diffrn_orient_matrix_UB_22      0.0476122000
_diffrn_orient_matrix_UB_23      0.0090218000
_diffrn_orient_matrix_UB_31      0.0202244000
_diffrn_orient_matrix_UB_32      0.0210514000
_diffrn_orient_matrix_UB_33      -0.0370010000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0553
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            22593
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.924
_diffrn_source                   'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.792
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38008
_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    1.561
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1312
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.539
_refine_diff_density_min         -1.400
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         11454
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0541
_refine_ls_R_factor_gt           0.0358
_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^)+(0.0285P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0669
_refine_ls_wR_factor_ref         0.0756
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8931
_reflns_number_total             11454
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01273_si_005.cif
_cod_data_source_block           180801_s1_csy
_cod_database_code               4514794
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         c12h12n2o3
_shelx_estimated_absorpt_t_max   0.380
_shelx_estimated_absorpt_t_min   0.285
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C16(H16), C18(H18), C19(H19), C20(H20),
 C21(H21), C36(H36), C37(H37), C38(H38), C39(H39), C48(H48), C50(H50), C51(H51),
  C52(H52), C53(H53)
2.b Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,
 H14C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C32(H32A,H32B,H32C), C41(H41A,H41B,H41C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C)
;
_shelx_res_checksum              72204
_shelx_hkl_checksum              55068
_olex2_submission_special_instructions 'No special instructions were received'