Catalytic asymmetric inverse-electron-demand aza-Diels–Alder reaction of 1,3-diazadienes with 3-vinylindoles
Miao, Yu-Hang; Hua, Yuan-Zhao; Gao, Hao-Jie; Mo, Nan-Nan; Wang, Mincan; Mei, Guang-Jian; Chemical Communications  (2022) –; doi:10.1039/D2CC02458F

data_7130188
_publ_section_title
;
 Catalytic asymmetric inverse-electron-demand aza-Diels--Alder reaction of
 1,3-diazadienes with 3-vinylindoles
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC02458F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H21 N3 O S, C H2 Cl2'
_chemical_formula_sum            'C29 H23 Cl2 N3 O S'
_chemical_formula_weight         532.46
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-03-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-04-19 deposited with the CCDC.	2022-06-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.916(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.7321(2)
_cell_length_b                   15.7556(4)
_cell_length_c                   9.1821(2)
_cell_measurement_reflns_used    2829
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      68.0450
_cell_measurement_theta_min      5.5870
_cell_volume                     1240.41(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7b (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_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.968
_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     31.00  58.00   0.50    0.50    --    0.00  57.00-180.00   54
  2  \w    -28.00  17.00   0.50    0.50    --    0.00  57.00-180.00   90
  3  \w     26.00  85.00   0.50    0.50    --    0.00  38.00 -90.00  118
  4  \w    -27.00  11.00   0.50    0.50    --    0.00  57.00  60.00   76
  5  \w     -8.00  22.00   0.50    0.50    --    0.00  38.00 -90.00   60
  6  \w     65.00 169.00   0.50    2.36    --   98.80  77.00-180.00  208
  7  \w     73.00 174.00   0.50    2.36    --   98.80  45.00  90.00  202
  8  \w     29.00  58.00   0.50    2.36    --   98.80 -45.00 -30.00   58
  9  \w     76.00 168.00   0.50    2.36    --   98.80  45.00 150.00  184
 10  \w     78.00 182.00   0.50    2.36    --   98.80  45.00 120.00  208
 11  \w     43.00 123.00   0.50    2.36    --   98.80 -82.00  60.00  160
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0866005000
_diffrn_orient_matrix_UB_12      -0.0566046000
_diffrn_orient_matrix_UB_13      -0.1257563000
_diffrn_orient_matrix_UB_21      -0.1487180000
_diffrn_orient_matrix_UB_22      0.0055549000
_diffrn_orient_matrix_UB_23      0.0668490000
_diffrn_orient_matrix_UB_31      -0.0513140000
_diffrn_orient_matrix_UB_32      0.0795163000
_diffrn_orient_matrix_UB_33      -0.0945952000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0196
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       5
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            5102
_diffrn_reflns_point_group_measured_fraction_full 0.743
_diffrn_reflns_point_group_measured_fraction_max 0.740
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.217
_diffrn_reflns_theta_min         5.654
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.369
_exptl_absorpt_correction_T_max  0.90400
_exptl_absorpt_correction_T_min  0.86800
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7b (Rigaku Oxford Diffraction, 2015)
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    1.426
_exptl_crystal_description       block
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.045
_exptl_crystal_size_mid          0.035
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.821
_refine_diff_density_min         -0.923
_refine_diff_density_rms         0.123
_refine_ls_abs_structure_details
;
 Flack x determined using 914 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.033(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         3364
_refine_ls_number_restraints     89
_refine_ls_restrained_S_all      1.251
_refine_ls_R_factor_all          0.0987
_refine_ls_R_factor_gt           0.0938
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2428
_refine_ls_wR_factor_ref         0.2506
_reflns_Friedel_coverage         0.470
_reflns_Friedel_fraction_full    0.499
_reflns_Friedel_fraction_max     0.493
_reflns_number_gt                3103
_reflns_number_total             4544
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02458f2.cif
_cod_data_source_block           20220219a1-1
_cod_database_code               7130188
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H O N S Ag'
_chemical_oxdiff_usercomment     ' '
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.863
_reflns_odcompleteness_completeness 99.70
_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
2. Rigid bond restraints
 C25, C26, C27, O1, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C22, C20, C19, C24, C23
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C20 \\sim C19 \\sim C24 \\sim C23 \\sim C22 \\sim C21: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
C25 \\sim C26 \\sim C27 \\sim O1 \\sim C28: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3A), C4(H4)
4.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B)
4.c Aromatic/amide H refined with riding coordinates:
 N3(H3), C17(H17), C11(H11), C10(H10), C24(H24), C16(H16), C14(H14), C15(H15),
 C23(H23), C26(H26), C9(H9), C7(H7), C8(H8), C28(H28), C20(H20), C22(H22),
 C27(H27), C21(H21)
;
_shelx_res_checksum              43503
_shelx_hkl_checksum              7344
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.169
_oxdiff_exptl_absorpt_empirical_full_min 0.906