Synthesis of Chiral Bis(3-indolyl)methanes Bearing a Trifluoromethylated All-Carbon Quaternary Stereocenter via Nickel-Catalyzed Asymmetric Friedel-Crafts Alkylation Reaction.
Zhu, Wen-Jing; Gong, Jun-Fang; Song, Mao-Ping; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00336

data_4038590
_publ_section_title
;
 Synthesis of Chiral Bis(3-indolyl)methanes Bearing a Trifluoromethylated
 All-Carbon Quaternary Stereocenter via Nickel-Catalyzed Asymmetric
 Friedel-Crafts Alkylation Reaction.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00336
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H16 F3 N3 O2'
_chemical_formula_sum            'C20 H16 F3 N3 O2'
_chemical_formula_weight         387.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-06-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   6.8083(6)
_cell_length_b                   15.0243(10)
_cell_length_c                   34.886(2)
_cell_measurement_reflns_used    10172
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.1230
_cell_measurement_theta_min      4.7820
_cell_volume                     3568.5(4)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details
;
  1 omega -106.00    2.00   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -19.0000   90.0000 225

  2 omega  -46.00  -20.56   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000 -180.0000 53

  3 omega  -97.00  -22.60   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000   30.0000 155

  4 omega   60.00   98.88   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -150.0000 81

  5 omega    7.00   42.04   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   81.0000   15.5802 73

  6 omega   14.00   50.00   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -30.0000 75

  7 omega   22.00   48.40   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
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  8 omega   21.00   58.44   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000   60.0000 78

  9 omega  -31.00   -5.56   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  120.0000 53

 10 omega   70.00   96.88   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000    0.0000 56

 11 omega  -36.00   61.44   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -19.0000    0.0000 203

 12 omega   62.00   88.88   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   60.0000 56

 13 omega   29.00   55.40   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -90.0000 55

 14 omega   68.00  105.92   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -30.0000 79

 15 omega   18.00   89.04   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -30.0000 148

 16 omega   77.00  103.88   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000 -120.0000 56

 17 omega   57.00   86.76   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   30.0000 62

 18 omega    8.00   34.40   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000   60.0000 55

 19 omega   24.00   63.36   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  120.0000 82

 20 omega   59.00  103.16   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -90.0000 92

 21 omega   33.00   70.44   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
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 22 omega   80.00  105.44   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000   60.0000 53

 23 omega   65.00  106.76   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  120.0000 87

 24 omega   73.00  106.60   0.4800    4.2500
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -120.0000 70

 25 omega  139.00  165.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 55

 26 omega   80.00  106.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   30.0000 56

 27 omega   79.00  105.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -90.0000 56

 28 omega   79.00  115.00   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 75

 29 omega   57.00  140.04   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  178.0000  120.0000 173

 30 omega   82.00  178.00   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -60.0000 200

 31 omega   38.00   85.04   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 98

 32 omega   89.00  116.36   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -120.0000 57

 33 omega   88.00  114.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -90.0000 56

 34 omega   87.00  113.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   63.0000  -37.1584 55

 35 omega  149.00  175.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 55

 36 omega   79.00  104.44   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -60.0000 53

 37 omega  151.00  177.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 55

 38 omega   88.00  114.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -60.0000 56

 39 omega   79.00  105.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 56

 40 omega   82.00  144.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000   30.0000 131

 41 omega  112.00  175.84   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   60.0000 133

 42 omega   85.00  114.76   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000    0.0000 62

 43 omega   91.00  117.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 56

 44 omega  150.00  175.44   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -30.0000 53

 45 omega   92.00  120.32   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 59

 46 omega  144.00  176.16   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 67

 47 omega  108.00  134.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 55

 48 omega   47.00   95.00   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -60.0000 100

 49 omega   88.00  114.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000    0.0000 56

 50 omega   88.00  172.00   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -90.0000 175

 51 omega   88.00  114.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -90.0000 56

 52 omega   88.00  113.44   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000    0.0000 53

 53 omega   79.00  105.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 56

 54 omega   82.00  108.88   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -30.0000 56

 55 omega   40.00  126.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   90.0000 180

 56 omega  149.00  176.84   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 58

 57 omega   87.00  113.40   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
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 58 omega   86.00  105.68   0.4800   21.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   40.0000  -34.4367 41
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0713274000
_diffrn_orient_matrix_UB_12      -0.0469489000
_diffrn_orient_matrix_UB_13      -0.0367000000
_diffrn_orient_matrix_UB_21      0.0504410000
_diffrn_orient_matrix_UB_22      -0.0909594000
_diffrn_orient_matrix_UB_23      0.0178282000
_diffrn_orient_matrix_UB_31      -0.2091780000
_diffrn_orient_matrix_UB_32      -0.0059245000
_diffrn_orient_matrix_UB_33      0.0167542000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0432
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            33790
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.118
_diffrn_reflns_theta_max         67.118
_diffrn_reflns_theta_min         3.883
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.993
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58116
_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_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.442
_exptl_crystal_description       needle
_exptl_crystal_F_000             1600
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.339
_refine_diff_density_min         -0.178
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2013 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.04(8)
_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     507
_refine_ls_number_reflns         6355
_refine_ls_number_restraints     4
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0582
_refine_ls_R_factor_gt           0.0513
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0876P)^2^+0.3366P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1395
_refine_ls_wR_factor_ref         0.1455
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                5535
_reflns_number_total             6355
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00336_si_003.cif
_cod_data_source_block           201906161
_cod_original_cell_volume        3568.5(5)
_cod_database_code               4038590
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4F3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.841
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-O1
 1 with sigma of 0.02
 N1'-O2'
 1 with sigma of 0.02
 C1-N1
 1.45 with sigma of 0.02
 N1'-C1'
 1.45 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1'(H,HA)
3.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C16(H16), C17(H17),
 C19(H19), N2(H2), N3(H3), C4'(HB), C8'(HC), C9'(HD), C10'(HE), C11'(HF),
 C12'(HG), C16'(HH), C17'(HI), C19'(HJ), N2'(HN), N3'(HO)
3.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20'(HK,HL,HM)
;
_olex2_submission_special_instructions 'No special instructions were received'