Organocatalyzed Asymmetric Dearomative Aza-Michael/Michael Addition Cascade of 2-Nitrobenzofurans and 2-Nitrobenzothiophenes with 2-Aminochalcones.
Zhou, Xiao-Jian; Zhao, Jian-Qiang; Chen, Xin-Meng; Zhuo, Jun-Rui; Zhang, Yan-Ping; Chen, Yong-Zheng; Zhang, Xiao-Mei; Xu, Xiao-Ying; Yuan, Wei-Cheng; The Journal of organic chemistry 84 (2019) 4381–4391; doi:10.1021/acs.joc.9b00401

data_4034239
_publ_section_title
;
 Organocatalyzed Asymmetric Dearomative Aza-Michael/Michael Addition
 Cascade of 2-Nitrobenzofurans and 2-Nitrobenzothiophenes with
 2-Aminochalcones.
;
_journal_issue                   7
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4381
_journal_page_last               4391
_journal_paper_doi               10.1021/acs.joc.9b00401
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C30 H23 Cl N2 O6 S'
_chemical_formula_sum            'C30 H23 Cl N2 O6 S'
_chemical_formula_weight         575.01
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-25
_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                   20.2062(3)
_cell_length_b                   13.2940(2)
_cell_length_c                   10.06784(20)
_cell_measurement_reflns_used    3967
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7820
_cell_measurement_theta_min      3.9480
_cell_volume                     2704.44(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_details
;
  1 omega -106.00    4.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -19.0000 -180.0000 110

  2 omega   57.00  105.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -60.0000 48

  3 omega  -26.00   51.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  120.0000 77

  4 omega   27.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  -60.0000 26

  5 omega  -12.00   18.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  -60.0000 30

  6 omega  -32.00   35.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000   90.0000 67

  7 omega   58.00  107.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -30.0000 49

  8 omega   94.00  171.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  150.0000 77

  9 omega   55.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 33

 10 omega   39.00   75.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 36

 11 omega   55.00   81.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 26

 12 omega   45.00   91.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 46

 13 omega   41.00  128.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -61.0000   60.0000 87

 14 omega   41.00   67.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 26

 15 omega   65.00  177.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  120.0000 112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0148156000
_diffrn_orient_matrix_UB_12      0.1129045000
_diffrn_orient_matrix_UB_13      -0.0175099000
_diffrn_orient_matrix_UB_21      0.0537867000
_diffrn_orient_matrix_UB_22      0.0066956000
_diffrn_orient_matrix_UB_23      -0.1080994000
_diffrn_orient_matrix_UB_31      -0.0519686000
_diffrn_orient_matrix_UB_32      -0.0252587000
_diffrn_orient_matrix_UB_33      -0.1068590000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9921
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.952
_diffrn_reflns_theta_min         3.980
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.380
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90917
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.412
_exptl_crystal_description       prism
_exptl_crystal_F_000             1192
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.204
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1684 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(10)
_refine_ls_extinction_coef       0.0017(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     363
_refine_ls_number_reflns         5094
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0467
_refine_ls_R_factor_gt           0.0407
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0617P)^2^+0.0045P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1152
_reflns_Friedel_coverage         0.748
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.961
_reflns_number_gt                4542
_reflns_number_total             5094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00401_si_002.cif
_cod_data_source_block           201808348
_cod_database_code               4034239
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2Cl1
_shelx_estimated_absorpt_t_max   0.732
_shelx_estimated_absorpt_t_min   0.661
_reflns_odcompleteness_completeness 99.82
_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:
 C7(H7), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C12(H12), C13(H13), C14(H14), C15(H15), C19(H19),
 C20(H20), C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C28(H28), C29(H29)
2.d Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C)
;
_olex2_submission_special_instructions 'No special instructions were received'