Chiral phosphoric acid-catalyzed direct asymmetric mannich reaction of cyclic C-acylimines with simple ketones: facile access to C2-quaternary indolin-3-ones.
Li, Jin-Shan; Liu, Yong-Jie; Li, Shen; Ma, Jun-An; Chemical communications (Cambridge, England) 54 (2018) 9151–9154; doi:10.1039/c8cc05125a

data_7124488
_publ_section_title
;
 Chiral phosphoric acid-catalyzed direct asymmetric mannich reaction of
 cyclic C-acylimines with simple ketones: facile access to C2-quaternary
 indolin-3-ones.
;
_journal_issue                   66
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9151
_journal_page_last               9154
_journal_paper_doi               10.1039/c8cc05125a
_journal_volume                  54
_journal_year                    2018
_chemical_absolute_configuration R
_chemical_formula_moiety         'C20 H15 N O2 S, C2 H6 O S'
_chemical_formula_sum            'C22 H21 N O3 S2'
_chemical_formula_weight         411.52
_chemical_name_systematic        C22H22NO3S2
_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_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-07-02 deposited with the CCDC.
2018-07-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.94450(9)
_cell_length_b                   10.19612(12)
_cell_length_c                   25.8377(2)
_cell_measurement_reflns_used    26281
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      74.1400
_cell_measurement_theta_min      4.6310
_cell_volume                     2092.93(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1975
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     -8.00  18.00   1.00    6.17    --   34.00 101.00 -81.09   26
  2  \w      0.00  28.00   1.00    6.17    --   38.00  92.00  63.47   28
  3  \w    -69.00  32.00   1.00    6.17    --  -41.12  57.00-150.00  101
  4  \w   -113.00 -13.00   1.00    6.17    --  -41.12 -57.00-180.00  100
  5  \w   -116.00 -17.00   1.00    6.17    --  -41.12 -37.00-120.00   99
  6  \w    -96.00  -2.00   1.00    6.17    --  -41.12 125.00  30.00   94
  7  \w   -113.00 -13.00   1.00    6.17    --  -41.12 -57.00  60.00  100
  8  \w     23.00  97.00   1.00    6.17    --   41.12-125.00 -30.00   74
  9  \w      6.00  33.00   1.00    6.17    --   42.00  88.00 -35.32   27
 10  \w     21.00  47.00   1.00    6.17    --   54.00  79.00  37.81   26
 11  \w     21.00  47.00   1.00    6.17    --   54.00  79.00 -14.17   26
 12  \w     21.00  47.00   1.00    6.17    --   54.00  79.00 160.04   26
 13  \w     21.00  47.00   1.00    6.17    --   54.00  79.00 -80.54   26
 14  \w     20.00  46.00   1.00    6.17    --   54.00  81.00  98.15   26
 15  \w     26.00 133.00   1.00    6.17    --   58.00  75.00-127.59  107
 16  \w     33.00 142.00   1.00    6.17    --   66.00  77.00 154.00  109
 17  \w     33.00 142.00   1.00    6.17    --   66.00  77.00  65.39  109
 18  \w     34.00 141.00   1.00    6.17    --   66.00  75.00 -67.07  107
 19  \w     34.00 141.00   1.00    6.17    --   66.00  75.00-163.82  107
 20  \w     34.00 142.00   1.00    6.17    --   66.00  76.00-104.12  108
 21  \w     37.00 146.00   1.00    6.17    --   70.00  77.00  93.49  109
 22  \w     37.00 146.00   1.00    6.17    --   70.00  77.00  14.10  109
 23  \w     37.00 146.00   1.00    6.17    --   70.00  77.00 -31.31  109
 24  \w     49.00 158.00   1.00   24.67    --   82.00  77.00-150.36  109
 25  \w     58.00 157.00   1.00   24.67    --   90.00  76.00-139.91   99
 26  \w     75.00 168.00   1.00   24.67    --  107.82  77.00 -30.00   93
 27  \w     75.00 172.00   1.00   24.67    --  107.82  77.00 -60.00   97
 28  \w    134.00 160.00   1.00   24.67    --  107.82  61.00-120.00   26
 29  \w     80.00 111.00   1.00   24.67    --  107.82  61.00-120.00   31
 30  \w    119.00 173.00   1.00   24.67    --  107.82 125.00  90.00   54
 31  \w     35.00 120.00   1.00   24.67    --  107.82-125.00 -60.00   85
 32  \w     75.00 128.00   1.00   24.67    --  107.82  77.00  90.00   53
 33  \w     75.00 150.00   1.00   24.67    --  107.82  77.00-180.00   75
 34  \w     94.00 175.00   1.00   24.67    --  107.82 125.00-150.00   81
 35  \w     75.00 143.00   1.00   24.67    --  107.82  77.00 150.00   68
 36  \w     78.00 118.00   1.00   24.67    --  107.82  77.00-120.00   40
 37  \w     75.00 155.00   1.00   24.67    --  107.82  77.00 -90.00   80
 38  \w     75.00 176.00   1.00   24.67    --  107.82  77.00 120.00  101
 39  \w     32.00 121.00   1.00   24.67    --  107.82 -77.00 120.00   89
 40  \w     76.00 176.00   1.00   24.67    --  107.82  77.00   0.00  100
 41  \w     79.00 122.00   1.00   24.67    --  107.82  61.00  60.00   43
 42  \w     39.00 122.00   1.00   24.67    --  107.82-125.00  60.00   83
 43  \w     79.00 105.00   1.00   24.67    --  107.82  61.00  90.00   26
 44  \w     75.00 178.00   1.00   24.67    --  107.82  77.00  60.00  103
 45  \w     95.00 159.00   1.00   24.67    --  107.82 125.00-180.00   64
 46  \w    124.00 150.00   1.00   24.67    --  107.82  77.00  30.00   26
 47  \w     75.00 101.00   1.00   24.67    --  107.82  77.00  30.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0821708000
_diffrn_orient_matrix_UB_12      0.0667086000
_diffrn_orient_matrix_UB_13      -0.0471505000
_diffrn_orient_matrix_UB_21      0.1523193000
_diffrn_orient_matrix_UB_22      -0.0386380000
_diffrn_orient_matrix_UB_23      -0.0336089000
_diffrn_orient_matrix_UB_31      -0.0874926000
_diffrn_orient_matrix_UB_32      -0.1299401000
_diffrn_orient_matrix_UB_33      -0.0142180000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0104
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            43576
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.592
_diffrn_reflns_theta_max         66.592
_diffrn_reflns_theta_min         3.421
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.488
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86200
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       plate
_exptl_crystal_F_000             864
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: DMSO'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 1495 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3709
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0337
_refine_ls_R_factor_gt           0.0327
_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^)+(0.0481P)^2^+0.5904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                3599
_reflns_number_total             3709
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05125a3.cif
_cod_data_source_block           chq_0629
_cod_original_cell_volume        2092.94(4)
_cod_database_code               7124488
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C22H24NO3S2
_reflns_odcompleteness_completeness 99.95
_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.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C18(H18), C5(H5), C8(H8), C6(H6), C19(H19), C20(H20), C7(H7),
 C10(H10), C11(H11), C14(H14), C12(H12), C13(H13)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C21(H21A,H21B,H21C)
;
_shelx_res_checksum              78820
_shelx_hkl_checksum              55909
_olex2_date_sample_data_collection 2018-06-29
_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 1.182
_oxdiff_exptl_absorpt_empirical_full_min 0.855