Photoredox-catalyzed intermolecular dearomative trifluoromethylcarboxylation of indoles and heteroanalogues with CO2 and fluorinated radical precursors
Yi, Yaping; Fan, Zhengning; Xi, Chanjuan; Green Chemistry 24 (2022) 7894–7899; doi:10.1039/D2GC03000D

data_7245546
_publ_section_title
;
 Photoredox-catalyzed intermolecular dearomative
 trifluoromethylcarboxylation of indoles and heteroanalogues with CO2 and
 fluorinated radical precursors
;
_journal_issue                   20
_journal_name_full               'Green Chemistry'
_journal_page_first              7894
_journal_page_last               7899
_journal_paper_doi               10.1039/D2GC03000D
_journal_volume                  24
_journal_year                    2022
_chemical_formula_moiety         'C16 H17 Cl F3 N O4'
_chemical_formula_sum            'C16 H17 Cl F3 N O4'
_chemical_formula_weight         379.76
_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             2022-04-25
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-07-13 deposited with the CCDC.	2022-09-22 downloaded from the CCDC.
;
_cell_angle_alpha                114.406(3)
_cell_angle_beta                 94.673(2)
_cell_angle_gamma                99.133(2)
_cell_formula_units_Z            2
_cell_length_a                   9.1441(2)
_cell_length_b                   10.1797(3)
_cell_length_c                   10.2607(3)
_cell_measurement_reflns_used    7836
_cell_measurement_temperature    170.00(11)
_cell_measurement_theta_max      75.9770
_cell_measurement_theta_min      4.8030
_cell_volume                     847.17(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.945
_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     87.00 156.00   0.50    0.05    --  107.36  77.00   0.00  138
  2  \w     65.00 117.00   0.50    0.05    --   47.45 147.00 102.00  104
  3  \w    104.00 131.00   0.50    0.05    --  107.36 124.00 -62.00   54
  4  \w    148.00 175.00   0.50    0.05    --  107.36  38.00-150.00   54
  5  \w    109.00 135.00   0.50    0.05    --  107.36  38.00-150.00   52
  6  \w     71.00 106.00   0.50    0.05    --  107.36 -99.00-180.00   70
  7  \w     48.00  73.00   0.50    0.05    --  107.36-124.00-141.00   50
  8  \w     56.00  81.00   0.50    0.05    --   47.45-124.00-141.00   50
  9  \w     47.00  73.00   0.50    0.05    --   47.45-147.00  53.00   52
 10  \w     36.00 121.00   0.50    0.05    --  107.36-147.00  53.00  170
 11  \w     37.00  65.00   0.50    0.05    --  107.36 -99.00  90.00   56
 12  \w     73.00 104.00   0.50    0.05    --  107.36 -99.00  90.00   62
 13  \w     67.00  94.00   0.50    0.05    --  107.36 -99.00  60.00   54
 14  \w     37.00  64.00   0.50    0.05    --  107.36 -99.00  60.00   54
 15  \w     36.00  95.00   0.50    0.05    --  107.36 -99.00  30.00  118
 16  \w     36.00  99.00   0.50    0.05    --  107.36 -99.00-150.00  126
 17  \w     79.00 105.00   0.50    0.05    --  107.36 -77.00-150.00   52
 18  \w     46.00  71.00   0.50    0.05    --  107.36 -77.00-150.00   50
 19  \w     41.00  68.00   0.50    0.05    --  107.36 -57.00  90.00   54
 20  \w     38.00  67.00   0.50    0.05    --  107.36 -57.00  60.00   58
 21  \w    -21.00  20.00   0.50    0.05    --  -47.45  19.00 120.00   82
 22  \w    -99.00 -65.00   0.50    0.05    --  -47.45 147.00 102.00   68
 23  \w   -127.00 -38.00   0.50    0.05    -- -104.50 147.00 102.00  178
 24  \w    -91.00 -47.00   0.50    0.05    --  -47.45 124.00 -62.00   88
 25  \w   -126.00 -72.00   0.50    0.05    -- -104.50 145.00-141.61  108
 26  \w    -90.00 -64.00   0.50    0.05    -- -104.50 124.00 -62.00   52
 27  \w    -21.00  23.00   0.50    0.05    --  -47.45  19.00 -30.00   88
 28  \w    -22.00  26.00   0.50    0.05    --  -47.45  19.00-150.00   96
 29  \w    -81.00 -55.00   0.50    0.05    -- -104.50  77.00-180.00   52
 30  \w    -62.00 -37.00   0.50    0.05    -- -104.50  57.00 -90.00   50
 31  \w    -62.00 -34.00   0.50    0.05    -- -104.50  57.00 -60.00   56
 32  \w    -58.00 -33.00   0.50    0.05    -- -104.50  57.00 150.00   50
 33  \w   -117.00 -25.00   0.50    0.05    --  -47.45 -77.00-120.00  184
 34  \w   -120.00 -94.00   0.50    0.05    -- -104.50 -19.00-150.00   52
 35  \w   -171.00-136.00   0.50    0.05    -- -104.50 -19.00-150.00   70
 36  \w   -173.00-124.00   0.50    0.05    -- -104.50 -65.00 -65.60   98
 37  \w   -122.00 -95.00   0.50    0.05    -- -104.50 -65.00 -65.60   54
 38  \w   -174.00 -89.00   0.50    0.05    -- -104.50 -61.00 -37.15  170
 39  \w   -137.00-112.00   0.50    0.05    -- -104.50-147.00  53.00   50
 40  \w   -105.00 -78.00   0.50    0.05    --  -47.45-125.00  60.00   54
 41  \w   -118.00 -59.00   0.50    0.05    --  -47.45-147.00  53.00  118
 42  \w   -145.00 -88.00   0.50    0.05    -- -104.50-124.00-141.00  114
 43  \w   -173.00 -86.00   0.50    0.05    -- -104.50 -99.00-180.00  174
 44  \w   -100.00 -74.00   0.50    0.05    --  -47.45-125.00-150.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1591792000
_diffrn_orient_matrix_UB_12      -0.0284964000
_diffrn_orient_matrix_UB_13      0.0353563000
_diffrn_orient_matrix_UB_21      0.0652241000
_diffrn_orient_matrix_UB_22      0.0684238000
_diffrn_orient_matrix_UB_23      0.1627212000
_diffrn_orient_matrix_UB_31      -0.0180583000
_diffrn_orient_matrix_UB_32      0.1530483000
_diffrn_orient_matrix_UB_33      0.0142491000
_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  0.0216
_diffrn_reflns_av_unetI/netI     0.0207
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.945
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9766
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.347
_diffrn_reflns_theta_min         4.797
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.496
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86219
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       block
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.046
_refine_ls_extinction_coef       0.0022(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     231
_refine_ls_number_reflns         3386
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.093
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0523P)^2^+0.2174P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0921
_refine_ls_wR_factor_ref         0.0934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3147
_reflns_number_total             3386
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2gc03000d2.cif
_cod_data_source_block           tx10770
_cod_depositor_comments          'Adding full bibliography for 7245546.cif.'
_cod_original_cell_volume        847.16(4)
_cod_database_code               7245546
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N O F Cl'
_chemical_oxdiff_usercomment     ' '
_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 Ternary CH refined with riding coordinates:
 C2(H2), C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H3), C5(H4), C6(H5)
2.c Idealised Me refined as rotating group:
 C14(H12,H13,H14), C10(H6,H8,H7), C13(H9,H11,H10), C15(H16,H15,H17)
;
_shelx_res_checksum              99218
_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 1.387
_oxdiff_exptl_absorpt_empirical_full_min 0.788