Benzylidene succinimides as 3C synthons for the asymmetric tandem Mannich reaction/transamidation of cyclic trifluoromethyl ketimines to obtain F<sub>3</sub>C-containing polycyclic dihydroquinazolinones.
Zhang, Xia-Yan; Dou, Pei-Hao; Lu, Wen-Ya; You, Yong; Zhao, Jian-Qiang; Wang, Zhen-Hua; Yuan, Wei-Cheng; Chemical communications (Cambridge, England) 57 (2021) 2927–2930; doi:10.1039/d0cc08131k

data_7127912
_publ_section_title
;
 Benzylidene succinimides as 3C synthons for the asymmetric tandem Mannich
 reaction/transamidation of cyclic trifluoromethyl ketimines to obtain
 F<sub>3</sub>C-containing polycyclic dihydroquinazolinones.
;
_journal_issue                   23
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2927
_journal_page_last               2930
_journal_paper_doi               10.1039/d0cc08131k
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C33 H29 Cl F3 N3 O6'
_chemical_formula_sum            'C33 H29 Cl F3 N3 O6'
_chemical_formula_weight         656.04
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2020-05-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-11-24 deposited with the CCDC.	2021-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.913(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.5411(3)
_cell_length_b                   13.6581(5)
_cell_length_c                   12.6050(4)
_cell_measurement_reflns_used    6569
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      64.9180
_cell_measurement_theta_min      4.6370
_cell_volume                     1642.60(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_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    -56.00   8.00   0.50    4.50    --  -33.50  37.00-120.00  128
  2  \w    -68.00 -12.00   0.50    4.50    --  -33.50 -37.00   0.00  112
  3  \w     50.00 104.00   0.50    4.50    --   36.47  77.00  30.00  108
  4  \w     11.00  43.00   0.50    4.50    --   36.47  77.00  30.00   64
  5  \w     73.00 106.00   0.50    4.50    --   36.47 178.00 150.00   66
  6  \w     27.00 103.00   0.50    4.50    --   36.47  57.00 150.00  152
  7  \w     14.00  46.00   0.50    4.50    --   36.47  77.00 -30.00   64
  8  \w     75.00 103.00   0.50    4.50    --   36.47  77.00 -30.00   56
  9  \w     77.00 110.00   0.50   18.50    --  108.00 -94.00 -90.00   66
 10  \w     51.00 119.00   0.50   18.50    --  108.00 -45.00  90.00  136
 11  \w    134.00 160.00   0.50   18.50    --  108.00  45.00  90.00   52
 12  \w    100.00 128.00   0.50   18.50    --  108.00 -30.00  90.00   56
 13  \w     41.00 134.00   0.50   18.50    --  108.00 -30.00-180.00  186
 14  \w     43.00  89.00   0.50   18.50    --  108.00-111.00  30.00   92
 15  \w    140.00 178.00   0.50   18.50    --  108.00 111.00-150.00   76
 16  \w     37.00  76.00   0.50   18.50    --  108.00 -30.00  90.00   78
 17  \w     41.00 124.00   0.50   18.50    --  108.00 -61.00 -60.00  166
 18  \w     94.00 120.00   0.50   18.50    --  108.00  45.00  90.00   52
 19  \w    -49.00 -23.00   0.50   10.00    --  -33.50  57.00-150.00   52
 20  \w    -56.00 -23.00   0.50   10.00    --  -33.50  77.00  60.00   66
 21  \w      2.00  34.00   0.50   10.00    --  -33.50  57.00-150.00   64
 22  \w   -103.00 -49.00   0.50   10.00    --  -33.50 -37.00  60.00  108
 23  \w    -36.00 -11.00   0.50   10.00    --  -33.50 -37.00   0.00   50
 24  \w      6.00  32.00   0.50   10.00    --  -33.50  77.00  60.00   52
 25  \w     22.00  48.00   0.50   10.00    --   36.47  57.00  30.00   52
 26  \w      9.00  40.00   0.50   10.00    --   36.47  77.00 -90.00   62
 27  \w     25.00  65.00   0.50   10.00    --   36.47  37.00 120.00   80
 28  \w     -4.00  43.00   0.50   10.00    --   36.47 -99.00 -60.00   94
 29  \w     70.00  96.00   0.50   10.00    --   36.47  57.00 120.00   52
 30  \w     59.00  85.00   0.50   10.00    --   36.47  57.00  30.00   52
 31  \w     30.00  56.00   0.50   10.00    --   36.47  37.00 150.00   52
 32  \w     56.00  85.00   0.50   10.00    --   36.47  77.00 -30.00   58
 33  \w     26.00  55.00   0.50   10.00    --   36.47  57.00 120.00   58
 34  \w     57.00 108.00   0.50   10.00    --   36.47 178.00-150.00  102
 35  \w     66.00 102.00   0.50   10.00    --   36.47  19.00  60.00   72
 36  \w     52.00  77.00   0.50   10.00    --   36.47 -99.00 -60.00   50
 37  \w     64.00  90.00   0.50   10.00    --   36.47  57.00   0.00   52
 38  \w     28.00  54.00   0.50   10.00    --   36.47  57.00  60.00   52
 39  \w     79.00 105.00   0.50   17.50    --  108.00  77.00  30.00   52
 40  \w     79.00 105.00   0.50   17.50    --  108.00  77.00 -90.00   52
 41  \w     79.00 105.00   0.50   17.50    --  108.00  77.00   0.00   52
 42  \w    105.00 131.00   0.50   17.50    --  108.00  77.00 -60.00   52
 43  \w     77.00 102.00   0.50   17.50    --  108.00  15.00 -30.00   50
 44  \w     79.00 104.00   0.50   17.50    --  108.00  77.00 -60.00   50
 45  \w    136.00 162.00   0.50   17.50    --  108.00  30.00  60.00   52
 46  \w     82.00 132.00   0.50   17.50    --  108.00  30.00 -30.00  100
 47  \w     84.00 121.00   0.50   17.50    --  108.00  30.00   0.00   74
 48  \w     79.00 105.00   0.50   17.50    --  108.00  77.00  60.00   52
 49  \w     89.00 115.00   0.50   17.50    --  108.00  61.00  30.00   52
 50  \w     82.00 125.00   0.50   17.50    --  108.00  30.00  30.00   86
 51  \w    128.00 158.00   0.50   17.50    --  108.00  77.00 -30.00   60
 52  \w     62.00  88.00   0.50   17.50    --  108.00 -94.00-180.00   52
 53  \w     88.00 114.00   0.50   17.50    --  108.00  61.00 -60.00   52
 54  \w     79.00 104.00   0.50   17.50    --  108.00  77.00 -30.00   50
 55  \w     51.00  77.00   0.50   17.50    --  108.00 -94.00 -60.00   52
 56  \w     63.00 101.00   0.50   17.50    --  108.00  15.00  90.00   76
 57  \w     84.00 124.00   0.50   17.50    --  108.00  30.00 -60.00   80
 58  \w     88.00 113.00   0.50   17.50    --  108.00  61.00 -30.00   50
 59  \w     86.00 114.00   0.50   17.50    --  108.00  30.00  90.00   56
 60  \w     88.00 145.00   0.50   17.50    --  108.00  45.00   0.00  114
 61  \w     88.00 114.00   0.50   17.50    --  108.00  61.00 -90.00   52
 62  \w     90.00 118.00   0.50   17.50    --  108.00  45.00 -60.00   56
 63  \w     88.00 117.00   0.50   17.50    --  108.00  61.00  60.00   58
 64  \w     88.00 114.00   0.50   17.50    --  108.00  61.00   0.00   52
 65  \w    146.00 177.00   0.50   17.50    --  108.00  77.00   0.00   62
 66  \w     86.00 111.00   0.50   17.50    --  108.00  30.00  60.00   50
 67  \w     70.00  96.00   0.50   17.50    --  108.00  15.00   0.00   52
 68  \w    -36.00 -11.00   0.50   10.00    --  -33.50 -37.00   0.00   50
 69  \w     13.00  39.00   0.50   10.00    --   36.47  77.00 -90.00   52
 70  \w     34.00  60.00   0.50   10.00    --   36.47  37.00 120.00   52
 71  \w     22.00  48.00   0.50   10.00    --   36.47  57.00  30.00   52
 72  \w     66.00 102.00   0.50   10.00    --   36.47  19.00  60.00   72
 73  \w     75.00 101.00   0.50   10.00    --   36.47  37.00   0.00   52
 74  \w     53.00  79.00   0.50   10.00    --   36.47  57.00 -90.00   52
 75  \w     33.00  67.00   0.50   10.00    --   36.47  77.00  60.00   68
 76  \w     93.00 119.00   0.50   17.50    --  108.00  61.00   0.00   52
 77  \w     83.00 109.00   0.50   17.50    --  108.00  15.00  90.00   52
 78  \w     93.00 119.00   0.50   17.50    --  108.00  61.00 -60.00   52
 79  \w    -36.00 -11.00   0.50   10.00    --  -33.50 -37.00   0.00   50
 80  \w     13.00  39.00   0.50   10.00    --   36.47  77.00 -90.00   52
 81  \w     22.00  48.00   0.50   10.00    --   36.47  57.00  30.00   52
 82  \w     75.00 101.00   0.50   10.00    --   36.47  37.00   0.00   52
 83  \w     34.00  60.00   0.50   10.00    --   36.47  37.00 120.00   52
 84  \w     66.00 102.00   0.50   10.00    --   36.47  19.00  60.00   72
 85  \w     93.00 119.00   0.50   17.50    --  108.00  61.00 -60.00   52
 86  \w     83.00 109.00   0.50   17.50    --  108.00  15.00  90.00   52
 87  \w     93.00 119.00   0.50   17.50    --  108.00  61.00   0.00   52
 88  \w    -36.00 -11.00   0.50   10.00    --  -33.50 -37.00   0.00   50
 89  \w     13.00  39.00   0.50   10.00    --   36.47  77.00 -90.00   52
 90  \w     22.00  48.00   0.50   10.00    --   36.47  57.00  30.00   52
 91  \w     75.00 101.00   0.50   10.00    --   36.47  37.00   0.00   52
 92  \w     34.00  60.00   0.50   10.00    --   36.47  37.00 120.00   52
 93  \w     66.00 102.00   0.50   10.00    --   36.47  19.00  60.00   72
 94  \w     93.00 119.00   0.50   17.50    --  108.00  61.00 -60.00   52
 95  \w     83.00 109.00   0.50   17.50    --  108.00  15.00  90.00   52
 96  \w     93.00 119.00   0.50   17.50    --  108.00  61.00   0.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1304015000
_diffrn_orient_matrix_UB_12      0.0278349000
_diffrn_orient_matrix_UB_13      -0.0656284000
_diffrn_orient_matrix_UB_21      -0.0886222000
_diffrn_orient_matrix_UB_22      -0.0019576000
_diffrn_orient_matrix_UB_23      -0.1020143000
_diffrn_orient_matrix_UB_31      -0.0348821000
_diffrn_orient_matrix_UB_32      0.1092988000
_diffrn_orient_matrix_UB_33      0.0147842000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            21371
_diffrn_reflns_point_group_measured_fraction_full 0.913
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        67.060
_diffrn_reflns_theta_max         67.060
_diffrn_reflns_theta_min         3.506
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.590
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85575
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.326
_exptl_crystal_description       prism
_exptl_crystal_F_000             680
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.163
_refine_diff_density_min         -0.159
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1507 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     431
_refine_ls_number_reflns         5348
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0578
_refine_ls_R_factor_gt           0.0481
_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^)+(0.0805P)^2^+0.0330P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1274
_refine_ls_wR_factor_ref         0.1360
_reflns_Friedel_coverage         0.745
_reflns_Friedel_fraction_full    0.817
_reflns_Friedel_fraction_max     0.817
_reflns_number_gt                4444
_reflns_number_total             5348
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc08131k2.cif
_cod_data_source_block           20200529
_cod_depositor_comments
'Adding full bibliography for 7127911--7127912.cif.'
_cod_original_cell_volume        1642.60(10)
_cod_database_code               7127912
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4Cl1
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.763
_reflns_odcompleteness_completeness 99.97
_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. Restrained distances
 O6A-C33A
 1.55 with sigma of 0.02
 O6-C33
 1.55 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C33) \\sim Ueq, Uanis(C33A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O6) = Uanis(O6A)
Uanis(C33) = Uanis(C33A)
4. Others
 Sof(O6A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(1)
 Sof(O6)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C4(H4)
5.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C11(H11), C13(H13), C15(H15), C16(H16), C17(H17), C18(H18),
 C19(H19), C28(H28), C29(H29), C31(H31), C32(H32)
5.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C33(H33A,H33B,
 H33C), C33A(H33D,H33E,H33F)
;
_shelx_res_checksum              94907
_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 1.651
_oxdiff_exptl_absorpt_empirical_full_min 0.810