Organocatalytic 1,4-Addition of Azadienes with 3-Homoacyl Coumarins toward Highly Enantioenriched Benzofuran Coumarin Skeletons.
Yan, Juzhang; Li, Xiaoping; Chen, Yuzhen; Li, Ying; Chen, Weiwen; Zhan, Ruoting; Huang, Huicai; The Journal of organic chemistry 85 (2020) 12175–12186; doi:10.1021/acs.joc.0c01379

data_4038791
_publ_section_title
;
 Organocatalytic 1,4-Addition of Azadienes with 3-Homoacyl Coumarins
 toward Highly Enantioenriched Benzofuran Coumarin Skeletons.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              12175
_journal_page_last               12186
_journal_paper_doi               10.1021/acs.joc.0c01379
_journal_volume                  85
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C39 H28 Br N O6 S'
_chemical_formula_sum            'C39 H28 Br N O6 S'
_chemical_formula_weight         718.59
_space_group_crystal_system      tetragonal
_space_group_IT_number           92
_space_group_name_Hall           'P 4abw 2nw'
_space_group_name_H-M_alt        'P 41 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-01-24
_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            8
_cell_length_a                   23.9795(3)
_cell_length_b                   23.9795(3)
_cell_length_c                   13.6928(2)
_cell_measurement_reflns_used    9759
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      74.7380
_cell_measurement_theta_min      2.5940
_cell_volume                     7873.58(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_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      99.98(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.965
_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    -25.00  66.00   0.50    0.30    --   46.62 -83.00 108.00  182
  2  \w     60.00 133.00   0.50    2.50    --  106.69 -83.00 108.00  146
  3  \w     38.00  68.00   0.50    2.50    --  106.69 -61.00  90.00   60
  4  \w     36.00  62.00   0.50    2.50    --  106.69 -61.00  30.00   52
  5  \w     34.00  69.00   0.50    2.50    --  106.69 -61.00 120.00   70
  6  \w     76.00 128.00   0.50    2.50    --  106.69 -82.00-144.00  104
  7  \w    -66.00 -30.00   0.50    2.50    -- -102.00  61.00-150.00   72
  8  \w    -66.00 -39.00   0.50    2.50    -- -102.00  61.00 -30.00   54
  9  \w    -69.00 -34.00   0.50    2.50    -- -102.00  61.00  30.00   70
 10  \w    -68.00 -31.00   0.50    2.50    -- -102.00  61.00  60.00   74
 11  \w   -102.00 -77.00   0.50    0.30    --  -46.62-125.00  90.00   50
 12  \w   -106.00 -71.00   0.50    0.30    --  -46.62-125.00-120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0059836000
_diffrn_orient_matrix_UB_12      -0.0316713000
_diffrn_orient_matrix_UB_13      0.0973219000
_diffrn_orient_matrix_UB_21      0.0556660000
_diffrn_orient_matrix_UB_22      -0.0300788000
_diffrn_orient_matrix_UB_23      -0.0195266000
_diffrn_orient_matrix_UB_31      0.0314902000
_diffrn_orient_matrix_UB_32      0.0471156000
_diffrn_orient_matrix_UB_33      0.0529570000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1364
_diffrn_reflns_av_unetI/netI     0.1079
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            25938
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.068
_diffrn_reflns_theta_min         2.606
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.265
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56912
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
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    1.212
_exptl_crystal_description       block
_exptl_crystal_F_000             2944
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.934
_refine_diff_density_min         -0.789
_refine_diff_density_rms         0.175
_refine_ls_abs_structure_details
;
 Flack x determined using 2192 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     434
_refine_ls_number_reflns         7890
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.1017
_refine_ls_R_factor_gt           0.0884
_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^)+(0.1762P)^2^+1.7563P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2383
_refine_ls_wR_factor_ref         0.2515
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.922
_reflns_number_gt                6524
_reflns_number_total             7890
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01379_si_001.cif
_cod_data_source_block           jz01-2_sqd
_cod_depositor_comments          'Adding full bibliography for 4038791.cif.'
_cod_original_cell_volume        7873.6(2)
_cod_database_code               4038791
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.805
_shelx_estimated_absorpt_t_min   0.660
_reflns_odcompleteness_completeness 99.88
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Riding coordinates:
 N1(H1)
2.b Ternary CH refined with riding coordinates:
 C18(H18), C10(H10)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C34(H34), C24(H24), C28(H28), C23(H23), C37(H37), C38(H38), C20(H20),
 C4(H4), C17(H17), C3(H3), C5(H5), C16(H16), C13(H13), C15(H15), C31(H31),
 C35(H35), C21(H21), C29(H29), C30(H30), C2(H2), C14(H14)
2.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C)
;
_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 2.850
_oxdiff_exptl_absorpt_empirical_full_min 0.190
_platon_squeeze_void_probe_radius 1.20