A bifunctional pyrazolone–chromone synthon directed organocatalytic double Michael cascade reaction: forging five stereocenters in structurally diverse hexahydroxanthones
Liu, Xiong-Li; Zuo, Xiong; Wang, Jun-Xin; Chang, Shun-qin; Wei, Qi-Di; Zhou, Ying; Organic Chemistry Frontiers 6 (2019) 1485–; doi:10.1039/C9QO00265K

data_1554811
_publ_section_title
;
 A bifunctional pyrazolone--chromone synthon directed organocatalytic
 double Michael cascade reaction: forging five stereocenters in
 structurally diverse hexahydroxanthones
;
_journal_issue                   9
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1485
_journal_paper_doi               10.1039/C9QO00265K
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H30 N2 O7'
_chemical_formula_sum            'C34 H30 N2 O7'
_chemical_formula_weight         578.60
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-08-17 deposited with the CCDC.	2019-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.72120(10)
_cell_length_b                   10.32080(10)
_cell_length_c                   28.5171(3)
_cell_measurement_reflns_used    30879
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4250
_cell_measurement_theta_min      3.0920
_cell_volume                     2861.14(5)
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -65.00  33.00   1.00    1.00    --  -40.92  38.00 -60.00   98
  2  \w     23.00  97.00   1.00    1.00    --   40.92-125.00-180.00   74
  3  \w     23.00  97.00   1.00    1.00    --   40.92-125.00 -60.00   74
  4  \w    100.00 178.00   1.00    1.00    --  106.95 111.00  30.00   78
  5  \w     25.00 109.00   1.00    1.00    --  106.95 -95.00   0.00   84
  6  \w     81.00 178.00   1.00    1.00    --  106.95  45.00-180.00   97
  7  \w    100.00 178.00   1.00    1.00    --  106.95 111.00 120.00   78
  8  \w     74.00 178.00   1.00    1.00    --  106.95  77.00  30.00  104
  9  \w     34.00 133.00   1.00    1.00    --  106.95 -45.00  30.00   99
 10  \w     30.00 116.00   1.00    1.00    --  106.95-111.00 150.00   86
 11  \w   -117.00  -8.00   1.00    1.00    --  -40.92 -77.00  30.00  109
 12  \w   -113.00 -13.00   1.00    1.00    --  -40.92 -57.00 150.00  100
 13  \w   -113.00 -13.00   1.00    1.00    --  -40.92 -57.00 -90.00  100
 14  \w     79.00 178.00   1.00    1.00    --  106.95  30.00 -90.00   99
 15  \w     78.00 178.00   1.00    1.00    --  106.95  61.00  90.00  100
 16  \w     74.00 178.00   1.00    1.00    --  106.95  77.00   0.00  104
 17  \w     74.00 178.00   1.00    1.00    --  106.95  77.00 120.00  104
 18  \w     74.00 178.00   1.00    1.00    --  106.95  77.00-180.00  104
 19  \w     78.00 178.00   1.00    1.00    --  106.95  61.00 -30.00  100
 20  \w    -69.00  32.00   1.00    1.00    --  -40.92  57.00  60.00  101
 21  \w   -117.00  -8.00   1.00    1.00    --  -40.92 -77.00 120.00  109
 22  \w      8.00 117.00   1.00    1.00    --   40.92  77.00 -60.00  109
 23  \w     25.00  52.00   1.00    1.00    --  106.95 -95.00-150.00   27
 24  \w     78.00 178.00   1.00    1.00    --  106.95  61.00 -60.00  100
;
_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      -0.0782820000
_diffrn_orient_matrix_UB_12      -0.1246424000
_diffrn_orient_matrix_UB_13      0.0131227000
_diffrn_orient_matrix_UB_21      0.0411564000
_diffrn_orient_matrix_UB_22      0.0187168000
_diffrn_orient_matrix_UB_23      0.0517446000
_diffrn_orient_matrix_UB_31      -0.1314535000
_diffrn_orient_matrix_UB_32      0.0799917000
_diffrn_orient_matrix_UB_33      0.0083617000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0174
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            37400
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.490
_diffrn_reflns_theta_min         3.099
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.776
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48845
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       block
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.150
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 2373 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     392
_refine_ls_number_reflns         5734
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0327
_refine_ls_R_factor_gt           0.0323
_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^)+(0.0521P)^2^+0.4120P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0810
_refine_ls_wR_factor_ref         0.0813
_reflns_Friedel_coverage         0.758
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                5643
_reflns_number_total             5734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00265k2.cif
_cod_data_source_block           zx-6a-c
_cod_database_code               1554811
_shelx_shelxl_version_number     2018/3
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C28(H28), C17(H17), C24(H24), C26(H26), C4(H4), C20(H20), C25(H25),
 C27(H27), C2(H2), C19(H19), C3(H3), C18(H18)
2.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C32(H32A,H32B,H32C), C34(H34A,H34B,
 H34C)
;
_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 2.130
_oxdiff_exptl_absorpt_empirical_full_min 0.520