Organocatalytic Discrimination of Non-Directing Aryl and Heteroaryl Groups: Enantioselective Synthesis of Bioactive Indole-Containing Triarylmethanes
Yan, Qiaolin; Duan, Meng; Chen, Cien; Deng, Zhiqin; Wu, Mandi; Yu, Peiyuan; He, Ming-Liang; Zhu, Guangyu; Houk, Kendall N.; Sun, Jianwei; Chemical Science  (2022) –; doi:10.1039/D2SC00636G

data_1566792
_publ_section_title
;
 Organocatalytic Discrimination of Non-Directing Aryl and Heteroaryl
 Groups: Enantioselective Synthesis of Bioactive Indole-Containing
 Triarylmethanes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00636G
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H17 N S'
_chemical_formula_sum            'C20 H17 N S'
_chemical_formula_weight         303.40
_chemical_name_systematic
R)-3-Methyl-2-(phenyl(thiophen-2-yl)methyl)-1H-indole
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2021-07-12
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.06.29 svn.r12e2184c for OlexSys, GUI svn.r6374)
;
_audit_update_record
;
2021-09-10 deposited with the CCDC.	2022-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                103.438(2)
_cell_angle_beta                 103.111(2)
_cell_angle_gamma                102.977(2)
_cell_formula_units_Z            2
_cell_length_a                   8.3698(2)
_cell_length_b                   8.6024(2)
_cell_length_c                   11.6963(2)
_cell_measurement_reflns_used    10014
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5550
_cell_measurement_theta_min      4.0640
_cell_volume                     762.79(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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     52.00  86.00   1.00    3.50    --   80.00  49.00   4.10   34
  2  \w    -70.00  34.00   1.00    2.00    --  -39.95  57.00   0.00  104
  3  \w   -115.00 -14.00   1.00    2.00    --  -39.95 -37.00-150.00  101
  4  \w      2.00  27.00   1.00    2.00    --   39.95  90.00 104.94   25
  5  \w      4.00  29.00   1.00    2.00    --   39.95  85.00  64.29   25
  6  \w     27.00  97.00   1.00    2.00    --   39.95-125.00 120.00   70
  7  \w     10.00  58.00   1.00    2.00    --   39.95  57.00   0.00   48
  8  \w     65.00 113.00   1.00    2.00    --   39.95  57.00   0.00   48
  9  \w     28.00  71.00   1.00    2.00    --   39.95-125.00 -90.00   43
 10  \w     13.00  40.00   1.00    2.00    --   44.00  79.00  -0.98   27
 11  \w     14.00  39.00   1.00    2.00    --   48.00  79.00-172.27   25
 12  \w     13.00  38.00   1.00    2.00    --   48.00  82.00-120.83   25
 13  \w     15.00  42.00   1.00    2.00    --   48.00  80.00 -52.13   27
 14  \w     74.00  99.00   1.00    2.00    --   56.00  71.00-134.02   25
 15  \w     24.00  55.00   1.00    2.00    --   56.00  71.00-134.02   31
 16  \w     25.00  52.00   1.00    2.00    --   56.00  69.00 127.18   27
 17  \w     28.00  53.00   1.00    2.00    --   60.00  73.00  26.71   25
 18  \w     84.00 130.00   1.00    2.00    --   60.00  73.00  26.71   46
 19  \w     91.00 125.00   1.00    2.00    --   60.00  73.00 -72.79   34
 20  \w     31.00  57.00   1.00    2.00    --   60.00  73.00 -72.79   26
 21  \w     31.00  70.00   1.00    2.00    --   64.00  74.00 -26.60   39
 22  \w    116.00 141.00   1.00    2.00    --   64.00  74.00 -26.60   25
 23  \w     35.00  68.00   1.00    2.00    --   68.00  72.00  54.53   33
 24  \w     42.00  74.00   1.00    2.00    --   68.00  74.00 164.99   32
 25  \w    106.00 133.00   1.00    2.00    --   68.00  74.00-135.83   27
 26  \w     35.00  76.00   1.00    2.00    --   68.00  74.00-135.83   41
 27  \w     39.00  79.00   1.00    2.00    --   72.00  73.00 152.06   40
 28  \w     44.00  86.00   1.00    2.00    --   76.00  69.00  91.60   42
 29  \w     44.00 138.00   1.00    2.00    --   76.00  69.00  46.67   94
 30  \w     53.00 102.00   1.00    3.50    --   84.00  62.00 130.28   49
 31  \w     71.00 102.00   1.00    3.50    --   96.00  44.00 -73.24   31
 32  \w    107.00 170.00   1.00    3.50    --   96.00  44.00 -73.24   63
 33  \w     39.00 108.00   1.00    3.50    --  113.00-111.00-120.00   69
 34  \w     81.00 109.00   1.00    3.50    --  113.00-111.00  30.00   28
 35  \w     39.00  77.00   1.00    3.50    --  113.00-111.00 120.00   38
 36  \w     83.00 173.00   1.00    3.50    --  113.00  61.00  60.00   90
 37  \w     84.00 157.00   1.00    3.50    --  113.00  61.00 -90.00   73
 38  \w    125.00 158.00   1.00    3.50    --  113.00  61.00  30.00   33
 39  \w     85.00 122.00   1.00    3.50    --  113.00  61.00 -30.00   37
 40  \w     84.00 111.00   1.00    3.50    --  113.00  61.00  30.00   27
 41  \w    130.00 165.00   1.00    3.50    --  113.00  61.00  90.00   35
 42  \w     83.00 117.00   1.00    3.50    --  113.00  61.00  90.00   34
 43  \w    124.00 160.00   1.00    3.50    --  113.00  61.00-150.00   36
 44  \w     83.00 109.00   1.00    3.50    --  113.00  61.00-150.00   26
 45  \w    105.00 169.00   1.00    3.50    --  113.00 111.00 -60.00   64
 46  \w     29.00 107.00   1.00    3.50    --  113.00 -94.00 150.00   78
 47  \w     41.00 142.00   1.00    3.50    --  113.00 -61.00 -90.00  101
 48  \w     83.00 178.00   1.00    3.50    --  113.00  61.00-120.00   95
 49  \w     29.00 107.00   1.00    3.50    --  113.00 -94.00 -90.00   78
 50  \w     84.00 151.00   1.00    3.50    --  113.00  61.00-180.00   67
 51  \w     81.00 108.00   1.00    3.50    --  113.00-111.00  90.00   27
 52  \w     83.00 172.00   1.00    3.50    --  113.00  61.00 120.00   89
 53  \w     91.00 117.00   1.00    3.50    --  113.00  45.00-180.00   26
 54  \w     91.00 116.00   1.00    3.50    --  113.00  45.00-120.00   25
 55  \w     83.00 165.00   1.00    3.50    --  113.00  61.00   0.00   82
 56  \w     38.00  78.00   1.00    3.50    --  113.00-111.00  90.00   40
 57  \w    129.00 156.00   1.00    3.50    --  113.00  61.00 -60.00   27
 58  \w     84.00 109.00   1.00    3.50    --  113.00-111.00 120.00   25
 59  \w     83.00 126.00   1.00    3.50    --  113.00  61.00 -60.00   43
 60  \w    127.00 173.00   1.00    3.50    --  113.00  61.00 150.00   46
 61  \w     83.00 110.00   1.00    3.50    --  113.00  61.00 150.00   27
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1134879000
_diffrn_orient_matrix_UB_12      -0.1828669000
_diffrn_orient_matrix_UB_13      -0.0435390000
_diffrn_orient_matrix_UB_21      0.1609104000
_diffrn_orient_matrix_UB_22      -0.0601823000
_diffrn_orient_matrix_UB_23      0.0062299000
_diffrn_orient_matrix_UB_31      0.0170853000
_diffrn_orient_matrix_UB_32      0.0041516000
_diffrn_orient_matrix_UB_33      0.1347024000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0204
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            12888
_diffrn_reflns_point_group_measured_fraction_full 0.945
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.828
_diffrn_reflns_theta_min         4.066
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           0.80
_diffrn_source_power             0.040
_diffrn_source_target            Cu
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91725
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
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    1.321
_exptl_crystal_description       block
_exptl_crystal_F_000             320
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexane and ethyl acetate'
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.713
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 2567 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.011(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     435
_refine_ls_number_reflns         5874
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.157
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0380
_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^)+(0.0580P)^2^+0.4374P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1012
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.891
_reflns_Friedel_fraction_max     0.838
_reflns_number_gt                5766
_reflns_number_total             5874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00636g2.cif
_cod_data_source_block           qyan1cult
_cod_database_code               1566792
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C20 H17 N O S'
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.759
_reflns_odcompleteness_completeness 99.83
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_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
 C2A-C1A = C2A-C3A = C2C-C1A = C4A-C2C
 1.4 with sigma of 0.02
 S1-C1 \\sim S1-C4 \\sim S1B-C1 \\sim S1B-C3
 with sigma of 0.02
 S1A-C1A \\sim S1A-C4A \\sim S1C-C1A \\sim S1C-C3A
 with sigma of 0.02
 C4A-C2C \\sim C2C-C1A \\sim C2A-C1A \\sim C3A-C2A
 with sigma of 0.02
 C4-C2B \\sim C2B-C1 \\sim C2-C1 \\sim C3-C2
 with sigma of 0.02
3. Restrained planarity
 S1A, C1A, C2A, C3A, C4A
 with sigma of 0.02
 S1C, C1A, C2C, C3A, C4A
 with sigma of 0.02
 S1B, C1, C2B, C3, C4
 with sigma of 0.02
 S1, C1, C2, C3, C4
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C2A) \\sim Ueq, Uanis(C2C) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C4A)
\\sim Ueq, Uanis(S1A) \\sim Ueq, Uanis(S1C) \\sim Ueq: with sigma of 0.002 and
sigma for terminal atoms of 0.003
Uanis(C2B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.005
5. Rigid body (RIGU) restrains
 S1A, C1A, C2A, C3A, C4A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1C, C1A, C2C, C3A, C4A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1B, C1, C2B, C3, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, C1, C2, C3, C4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: S1(0.9) S1B(0.1) C2(0.9) H2(0.9) C2B(0.1) H2B(0.1) H3A(0.9)
 H3B(0.1) H4A(0.9) H4B(0.1) S1A(0.5) S1C(0.5) C2A(0.5) H2A(0.5) C2C(0.5)
 H2C(0.5) H3AA(0.5) H3AB(0.5) H4AA(0.5) H4AB(0.5)
7.a Ternary CH refined with riding coordinates:
 C11(H11), C11A(H11A)
7.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C2B(H2B), C3(H3A), C3(H3B), C4(H4A), C4(H4B), C6(H6), C7(H7),
 C8(H8), C9(H9), C10(H10), C15(H15), C16(H16), C17(H17), C18(H18), N1A(H1A),
 C2A(H2A), C2C(H2C), C3A(H3AA), C3A(H3AB), C4A(H4AA), C4A(H4AB), C6A(H6A),
 C7A(H7A), C8A(H8A), C9A(H9A), C10A(H10A), C15A(H15A), C16A(H16A), C17A(H17A),
 C18A(H18A)
7.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F)
;
_shelx_res_checksum              58139
_shelx_hkl_checksum              6730
_olex2_date_sample_data_collection 2021-07-11
_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 1.156
_oxdiff_exptl_absorpt_empirical_full_min 0.909