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_1566793
_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
(S)-3-Methyl-2-(phenyl(thiophen-3-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             2021-10-15
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-10-20 deposited with the CCDC.	2022-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                103.482(4)
_cell_angle_beta                 103.756(4)
_cell_angle_gamma                102.858(4)
_cell_formula_units_Z            2
_cell_length_a                   8.4366(4)
_cell_length_b                   8.5299(4)
_cell_length_c                   11.8199(6)
_cell_measurement_reflns_used    4268
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.1110
_cell_measurement_theta_min      4.0170
_cell_volume                     767.86(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1788
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.943
_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    120.00 170.00   1.00    2.50    --  113.00  77.00  60.00   50
  2  \w     10.00 105.00   1.00    1.00    --   39.95  57.00 -60.00   95
  3  \w     -7.00  64.00   1.00    1.00    --   39.95 -37.00  30.00   71
  4  \w     12.00  74.00   1.00    1.00    --   39.95 -77.00 -30.00   62
  5  \w     19.00 103.00   1.00    1.00    --   39.95  37.00-150.00   84
  6  \w    -34.00  -8.00   1.00    1.00    --   39.95 -37.00  30.00   26
  7  \w     68.00 109.00   1.00    2.50    --  113.00-111.00-120.00   41
  8  \w     34.00  91.00   1.00    2.50    --  113.00 -77.00 150.00   57
  9  \w     36.00  66.00   1.00    2.50    --  113.00-111.00-120.00   30
 10  \w     88.00 178.00   1.00    2.50    --  113.00  45.00  30.00   90
 11  \w     38.00 109.00   1.00    2.50    --  113.00-111.00  60.00   71
 12  \w     51.00 107.00   1.00    2.50    --  113.00 -94.00  90.00   56
 13  \w     38.00 146.00   1.00    2.50    --  113.00 -77.00-120.00  108
 14  \w     86.00 178.00   1.00    2.50    --  113.00  45.00 -30.00   92
 15  \w     38.00 138.00   1.00    2.50    --  113.00 -30.00   0.00  100
;
_diffrn_measurement_device       'kappa diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1082845000
_diffrn_orient_matrix_UB_12      -0.0200404000
_diffrn_orient_matrix_UB_13      0.1176353000
_diffrn_orient_matrix_UB_21      0.1126399000
_diffrn_orient_matrix_UB_22      0.1835208000
_diffrn_orient_matrix_UB_23      0.0350928000
_diffrn_orient_matrix_UB_31      -0.1194999000
_diffrn_orient_matrix_UB_32      0.0606891000
_diffrn_orient_matrix_UB_33      0.0688781000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0274
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            4569
_diffrn_reflns_point_group_measured_fraction_full 0.546
_diffrn_reflns_point_group_measured_fraction_max 0.528
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.202
_diffrn_reflns_theta_min         4.039
_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    1.811
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50162
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (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    1.312
_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          0.4
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.480
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.016(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     444
_refine_ls_number_reflns         3400
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0371
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0636P)^2^+0.3778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0964
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.119
_reflns_Friedel_fraction_full    0.123
_reflns_Friedel_fraction_max     0.112
_reflns_number_gt                3388
_reflns_number_total             3400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00636g2.cif
_cod_data_source_block           qyan2cult
_cod_original_cell_volume        767.85(7)
_cod_database_code               1566793
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C20 H18 O4'
_shelx_estimated_absorpt_t_max   0.773
_shelx_estimated_absorpt_t_min   0.531
_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
 C9-C6 \\sim C9-C7 \\sim C7-C8
 with sigma of 0.02
 C5-C4 \\sim C4-C3 \\sim C3-C2
 with sigma of 0.02
 S2-C6 \\sim S2-C8
 with sigma of 0.02
 S1-C5 \\sim S1-C2
 with sigma of 0.02
 C9-C1 \\sim C3-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(S1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of
0.005
Uanis(S2) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C6) \\sim
Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of
0.005
4. Rigid body (RIGU) restrains
 S2, C6, C7, C8, C9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, C2, C3, C4, C5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: S1(0.77) S2(0.23) H1A(0.77) H1B(0.23) C2(0.77) H2(0.77) C3(0.77)
 C4(0.77) H4(0.77) C5(0.77) H5(0.77) C6(0.23) H6(0.23) C7(0.23) H7(0.23)
 C8(0.23) H8(0.23) C9(0.23)
6.a Ternary CH refined with riding coordinates:
 C1(H1A), C1(H1B), C1A(H1AB)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C15(H15),
 C16(H16), C17(H17), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
 N1A(H1AA), C2A(H2A), C4A(H4A), C5A(H5A), C14A(H14A), C15A(H15A), C16A(H16A),
 C17A(H17A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A)
6.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C19A(H19D,H19E,H19F)
;
_shelx_res_checksum              15010
_shelx_hkl_checksum              89072
_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 1.686
_oxdiff_exptl_absorpt_empirical_full_min 0.458