Enantioselective Arylation of Tetrasubstituted Enamines: Access to Enantioenriched Indolenine and 1H-Indole Derivatives
Liang, Ren-Xiao; Zhong, Chao; Liu, Zhi-Hong; Yang, Miao; Tang, Heng-Wei; Chen, Jian-Fei; Yang, Yun-Fang; Jia, Yi-Xia; ACS Catalysis  (2021) 1827–1832; doi:10.1021/acscatal.0c05020

data_4518423
_publ_section_title
;
 Enantioselective Arylation of Tetrasubstituted Enamines: Access to
 Enantioenriched Indolenine and 1H-Indole Derivatives
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              1827
_journal_page_last               1832
_journal_paper_doi               10.1021/acscatal.0c05020
_journal_year                    2021
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C23 H27 N O4 S'
_chemical_formula_sum            'C23 H27 N O4 S'
_chemical_formula_weight         413.51
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-05
_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                120
_cell_formula_units_Z            6
_cell_length_a                   9.70670(10)
_cell_length_b                   9.70670(10)
_cell_length_c                   39.2119(3)
_cell_measurement_reflns_used    51218
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2780
_cell_measurement_theta_min      5.2290
_cell_volume                     3199.57(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.994
_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     27.00  53.00   1.00    1.00    --    0.00  12.00 -64.00   26
  2  \w     41.00  73.00   1.00    1.00    --   95.80 -12.00 123.00   32
  3  \w     79.00 124.00   1.00    1.00    --   95.80 -12.00 123.00   45
  4  \w     64.00  92.00   1.00    1.00    --   95.80  12.00 -64.00   28
  5  \w    -30.00  44.00   1.00    1.00    --    0.00  82.00-150.00   74
  6  \w    -19.00  31.00   1.00    1.00    --    0.00 -12.00 123.00   50
  7  \w    -88.00 -51.00   1.00    1.00    --    0.00 -38.00-120.00   37
  8  \w    -19.00  22.00   1.00    1.00    --    0.00  38.00-120.00   41
  9  \w    -89.00   5.00   1.00    1.00    --    0.00 -38.00   0.00   94
 10  \w    -23.00  30.00   1.00    1.00    --    0.00  57.00  60.00   53
 11  \w     19.00  45.00   1.00    1.00    --    0.00  57.00-180.00   26
 12  \w    -43.00   7.00   1.00    1.00    --    0.00 -38.00-120.00   50
 13  \w    -19.00  32.00   1.00    1.00    --    0.00  38.00 -60.00   51
 14  \w     25.00  50.00   1.00    1.00    --    0.00  19.00  30.00   25
 15  \w     53.00  85.00   1.00    1.00    --    0.00  82.00-150.00   32
 16  \w    -21.00  15.00   1.00    1.00    --    0.00  57.00-180.00   36
 17  \w     39.00  65.00   1.00    1.00    --    0.00  57.00  60.00   26
 18  \w     -8.00  78.00   1.00    1.00    --    0.00  77.00  90.00   86
 19  \w     55.00  89.00   1.00    1.00    --    0.00  38.00-120.00   34
 20  \w    -24.00   3.00   1.00    1.00    --    0.00  19.00  30.00   27
 21  \w     56.00 127.00   1.00    1.00    --   95.80 -82.00-120.00   71
 22  \w     10.00  49.00   1.00    1.00    --   95.80 -82.00-120.00   39
 23  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 24  \w     63.00  97.00   1.00    1.00    --   95.80  82.00 -90.00   34
 25  \w     69.00 147.00   1.00    1.00    --   95.80  66.00   2.48   78
 26  \w     63.00  88.00   1.00    1.00    --   95.80  81.00  89.90   25
 27  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 28  \w     63.00  96.00   1.00    1.00    --   95.80  81.00-165.56   33
 29  \w    134.00 160.00   1.00    1.00    --   95.80  45.00   0.00   26
 30  \w     71.00  97.00   1.00    1.00    --   95.80  61.00  60.00   26
 31  \w     58.00 128.00   1.00    1.00    --   95.80 -82.00 150.00   70
 32  \w     63.00  88.00   1.00    1.00    --   95.80  81.00  77.95   25
 33  \w    139.00 167.00   1.00    1.00    --   95.80  81.00  77.95   28
 34  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -30.00   25
 35  \w      6.00 128.00   1.00    1.00    --   95.80 -82.00 -60.00  122
 36  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 37  \w     69.00 184.00   1.00    1.00    --   95.80  65.00 -80.13  115
 38  \w    147.00 173.00   1.00    1.00    --   95.80  82.00-180.00   26
 39  \w     64.00  90.00   1.00    1.00    --   95.80  79.00-130.97   26
 40  \w    129.00 157.00   1.00    1.00    --   95.80  81.00  12.16   28
 41  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-180.00   26
 42  \w    100.00 185.00   1.00    1.00    --   95.80  82.00  30.00   85
 43  \w     93.00 127.00   1.00    1.00    --   95.80 -82.00   0.00   34
 44  \w     75.00 143.00   1.00    1.00    --   95.80  45.00  90.00   68
 45  \w     69.00 184.00   1.00    1.00    --   95.80  65.00-172.66  115
 46  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 47  \w    138.00 163.00   1.00    1.00    --   95.80  77.00   0.00   25
 48  \w     65.00 119.00   1.00    1.00    --   95.80  77.00  90.00   54
 49  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 120.00   26
 50  \w     75.00 145.00   1.00    1.00    --   95.80  45.00 -30.00   70
 51  \w     72.00 107.00   1.00    1.00    --   95.80  61.00 -90.00   35
 52  \w    129.00 169.00   1.00    1.00    --   95.80  61.00 -90.00   40
 53  \w     75.00 183.00   1.00    1.00    --   95.80  45.00-120.00  108
 54  \w     75.00 103.00   1.00    1.00    --   95.80  45.00   0.00   28
 55  \w     11.00  74.00   1.00    1.00    --   95.80 -82.00   0.00   63
 56  \w     72.00  98.00   1.00    1.00    --   95.80  56.00  85.98   26
 57  \w     63.00  99.00   1.00    1.00    --   95.80  81.00  12.16   36
 58  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 59  \w    128.00 185.00   1.00    1.00    --   95.80  82.00 -60.00   57
 60  \w    147.00 183.00   1.00    1.00    --   95.80  82.00 150.00   36
 61  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 62  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 63  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 64  \w     72.00 115.00   1.00    1.00    --   95.80  57.00-104.97   43
 65  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 66  \w     15.00  77.00   1.00    1.00    --   95.80 -82.00 -30.00   62
 67  \w    155.00 180.00   1.00    1.00    --   95.80  82.00-120.00   25
 68  \w    145.00 170.00   1.00    1.00    --   95.80  45.00-180.00   25
 69  \w     75.00 118.00   1.00    1.00    --   95.80  45.00-180.00   43
 70  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 71  \w     70.00  95.00   1.00    1.00    --   95.80  63.00  44.65   25
 72  \w     94.00 128.00   1.00    1.00    --   95.80 -82.00 -30.00   34
 73  \w      6.00 126.00   1.00    1.00    --   95.80 -82.00  90.00  120
 74  \w    107.00 176.00   1.00    1.00    --   95.80  77.00 -30.00   69
 75  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-150.00   25
 76  \w     74.00 100.00   1.00    1.00    --   95.80  49.00 136.76   26
 77  \w    115.00 185.00   1.00    1.00    --   95.80  49.00 136.76   70
 78  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 79  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  30.00   26
 80  \w     74.00 140.00   1.00    1.00    --   95.80  50.00 143.88   66
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1771877000
_diffrn_orient_matrix_UB_12      0.0542361000
_diffrn_orient_matrix_UB_13      -0.0053234000
_diffrn_orient_matrix_UB_21      -0.0418194000
_diffrn_orient_matrix_UB_22      -0.1749253000
_diffrn_orient_matrix_UB_23      -0.0030816000
_diffrn_orient_matrix_UB_31      -0.0210099000
_diffrn_orient_matrix_UB_32      0.0064600000
_diffrn_orient_matrix_UB_33      -0.0388065000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0107
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            86193
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.617
_diffrn_reflns_theta_min         5.262
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.584
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41959
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.288
_exptl_crystal_description       block
_exptl_crystal_F_000             1320
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.202
_refine_diff_density_min         -0.284
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1952 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(6)
_refine_ls_extinction_coef       0.00247(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     265
_refine_ls_number_reflns         4192
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0248
_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^)+(0.0313P)^2^+1.1141P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0632
_refine_ls_wR_factor_ref         0.0632
_reflns_Friedel_coverage         0.905
_reflns_Friedel_fraction_full    0.932
_reflns_Friedel_fraction_max     0.927
_reflns_number_gt                4187
_reflns_number_total             4192
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c05020_si_002.cif
_cod_data_source_block           exp_1087
_cod_original_cell_volume        3199.57(7)
_cod_database_code               4518423
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.599
_reflns_odcompleteness_completeness 99.85
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C21(H21)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12)
2.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              5940
_shelx_hkl_checksum              50212
_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 2.567
_oxdiff_exptl_absorpt_empirical_full_min 0.698