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_4518422
_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         'C19 H19 N O4 S'
_chemical_formula_sum            'C19 H19 N O4 S'
_chemical_formula_weight         357.43
_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'
_symmetry_Int_Tables_number      19
_atom_sites_solution_primary     dual
_audit_creation_date             2019-11-07
_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            4
_cell_length_a                   8.47740(10)
_cell_length_b                   10.98110(10)
_cell_length_c                   18.15540(10)
_cell_measurement_reflns_used    31421
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.2300
_cell_measurement_theta_min      4.0060
_cell_volume                     1690.11(3)
_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  'olex2.refine (Bourhis et al., 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 0.9973
_diffrn_measured_fraction_theta_max 0.9973
_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     -3.00  50.00   1.00    1.00    --    0.00  67.00-102.00   53
  2  \w    -32.00  -1.00   1.00    1.00    --    0.00 -67.00 123.00   31
  3  \w     73.00  98.00   1.00    1.00    --   95.80  67.00-102.00   25
  4  \w      6.00 122.00   1.00    1.00    --   95.80 -67.00 123.00  116
  5  \w    -18.00  68.00   1.00    1.00    --    0.00  38.00   0.00   86
  6  \w     50.00  77.00   1.00    1.00    --    0.00  82.00 -90.00   27
  7  \w    -19.00  41.00   1.00    1.00    --    0.00  38.00  90.00   60
  8  \w    -17.00  88.00   1.00    1.00    --    0.00  38.00  30.00  105
  9  \w    -21.00  18.00   1.00    1.00    --    0.00  57.00-150.00   39
 10  \w     28.00  89.00   1.00    1.00    --    0.00  38.00 150.00   61
 11  \w    -32.00  28.00   1.00    1.00    --    0.00  82.00 -90.00   60
 12  \w     23.00  89.00   1.00    1.00    --    0.00  57.00-150.00   66
 13  \w    -16.00  21.00   1.00    1.00    --    0.00  38.00 150.00   37
 14  \w    -25.00  16.00   1.00    1.00    --    0.00 -38.00  30.00   41
 15  \w    -12.00  13.00   1.00    1.00    --    0.00 -38.00 -90.00   25
 16  \w    -87.00 -51.00   1.00    1.00    --    0.00 -38.00 -90.00   36
 17  \w     64.00  89.00   1.00    1.00    --    0.00  38.00  90.00   25
 18  \w    125.00 151.00   1.00    1.00    --   95.80  82.00   0.00   26
 19  \w     64.00 116.00   1.00    1.00    --   95.80  82.00   0.00   52
 20  \w    149.00 174.00   1.00    1.00    --   95.80  82.00 -30.00   25
 21  \w    142.00 177.00   1.00    1.00    --   95.80  77.00 -90.00   35
 22  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 23  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 24  \w     43.00 123.00   1.00    1.00    --   95.80 -82.00 -60.00   80
 25  \w     66.00  92.00   1.00    1.00    --   95.80  74.00 119.44   26
 26  \w     64.00  90.00   1.00    1.00    --   95.80  82.00  30.00   26
 27  \w    126.00 152.00   1.00    1.00    --   95.80  74.00 119.44   26
 28  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 29  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  60.00   26
 30  \w     76.00 103.00   1.00    1.00    --   95.80  45.00 -30.00   27
 31  \w     67.00  93.00   1.00    1.00    --   95.80  71.00 -27.01   26
 32  \w     75.00 184.00   1.00    1.00    --   95.80  45.00   0.00  109
 33  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 34  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 35  \w    155.00 184.00   1.00    1.00    --   95.80  82.00  90.00   29
 36  \w     73.00 121.00   1.00    1.00    --   95.80  55.00 132.71   48
 37  \w    122.00 149.00   1.00    1.00    --   95.80  81.00 162.40   27
 38  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 39  \w    157.00 183.00   1.00    1.00    --   95.80  82.00-150.00   26
 40  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 41  \w    122.00 180.00   1.00    1.00    --   95.80  77.00 -60.00   58
 42  \w     63.00  89.00   1.00    1.00    --   95.80  81.00 162.40   26
 43  \w     63.00  95.00   1.00    1.00    --   95.80  82.00 -90.00   32
 44  \w     63.00  97.00   1.00    1.00    --   95.80  82.00 124.34   34
 45  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -60.00   26
 46  \w    132.00 185.00   1.00    1.00    --   95.80  55.00 132.71   53
 47  \w    137.00 172.00   1.00    1.00    --   95.80  67.00  94.36   35
 48  \w     10.00 102.00   1.00    1.00    --   95.80 -82.00  30.00   92
 49  \w     75.00 145.00   1.00    1.00    --   95.80  45.00 -90.00   70
 50  \w     76.00 185.00   1.00    1.00    --   95.80  61.00-150.00  109
 51  \w     79.00 116.00   1.00    1.00    --   95.80  45.00  60.00   37
 52  \w    122.00 185.00   1.00    1.00    --   95.80  45.00  60.00   63
 53  \w     64.00  90.00   1.00    1.00    --   95.80  80.00 -21.68   26
 54  \w    128.00 182.00   1.00    1.00    --   95.80  80.00 -21.68   54
 55  \w     77.00 124.00   1.00    1.00    --   95.80 -82.00-150.00   47
 56  \w     75.00 121.00   1.00    1.00    --   95.80  45.00-180.00   46
 57  \w     74.00 100.00   1.00    1.00    --   95.80  54.00 -24.17   26
 58  \w     20.00 128.00   1.00    1.00    --   95.80 -82.00   0.00  108
 59  \w    140.00 174.00   1.00    1.00    --   95.80  77.00  30.00   34
 60  \w     69.00 101.00   1.00    1.00    --   95.80  67.00  94.36   32
 61  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 62  \w     72.00 179.00   1.00    1.00    --   95.80  56.00 -73.19  107
 63  \w     73.00 178.00   1.00    1.00    --   95.80  53.00  78.33  105
 64  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  60.00   26
 65  \w     73.00 184.00   1.00    1.00    --   95.80  54.00-160.16  111
 66  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  30.00   26
 67  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 68  \w    160.00 185.00   1.00    1.00    --   95.80  82.00-180.00   25
 69  \w     89.00 118.00   1.00    1.00    --   95.80 -82.00  60.00   29
 70  \w     70.00 127.00   1.00    1.00    --   95.80 -82.00 150.00   57
 71  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-180.00   26
;
_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      0.0582494000
_diffrn_orient_matrix_UB_12      0.0806540000
_diffrn_orient_matrix_UB_13      -0.0637846000
_diffrn_orient_matrix_UB_21      0.1397207000
_diffrn_orient_matrix_UB_22      -0.0871894000
_diffrn_orient_matrix_UB_23      -0.0124655000
_diffrn_orient_matrix_UB_31      -0.1004554000
_diffrn_orient_matrix_UB_32      -0.0746788000
_diffrn_orient_matrix_UB_33      -0.0545864000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0161
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            41179
_diffrn_reflns_theta_full        67.0683
_diffrn_reflns_theta_max         67.07
_diffrn_reflns_theta_min         4.71
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.912
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31492
_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    1.4046
_exptl_crystal_description       block
_exptl_crystal_F_000             755.6815
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.1842
_refine_diff_density_min         -0.2730
_refine_diff_density_rms         0.0406
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0.020(12)
_refine_ls_d_res_high            0.8371
_refine_ls_d_res_low             9.3961
_refine_ls_goodness_of_fit_ref   1.0540
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    32
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3009
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0540
_refine_ls_R_factor_all          0.0229
_refine_ls_R_factor_gt           0.0227
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0335P)^2^+0.4242P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0587
_refine_ls_wR_factor_ref         0.0588
_reflns_Friedel_coverage         0.998
_reflns_limit_h_max              10
_reflns_limit_h_min              -10
_reflns_limit_k_max              13
_reflns_limit_k_min              -13
_reflns_limit_l_max              21
_reflns_limit_l_min              -21
_reflns_number_gt                2997
_reflns_number_total             3009
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs0c05020_si_003.cif
_cod_data_source_block           exp_1046
_cod_original_sg_symbol_Hall     ' P 2ac 2ab'
_cod_database_code               4518422
_reflns_odcompleteness_completeness 99.94
_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:
 C15(H15)
2.b Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C18(H18a,H18b)
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:
 C16(H16a,H16b,H16c), C7(H7a,H7b,H7c)
;
_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 3.071
_oxdiff_exptl_absorpt_empirical_full_min 0.616