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_1554812
_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         'C36 H32 F N3 O7'
_chemical_formula_sum            'C36 H32 F N3 O7'
_chemical_formula_weight         637.64
_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     direct
_audit_creation_date             2019-01-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-02-13 deposited with the CCDC.	2019-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.74660(10)
_cell_length_b                   12.2636(2)
_cell_length_c                   22.7319(2)
_cell_measurement_reflns_used    24932
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.3620
_cell_measurement_theta_min      1.9250
_cell_volume                     3269.89(7)
_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    'ShelXS (Sheldrick, 2008)'
_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 0.990
_diffrn_measured_fraction_theta_max 0.974
_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   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00 -60.00  100
  2  \w   -117.00  -8.00   1.00    1.00    --  -40.98 -77.00-180.00  109
  3  \w   -113.00 -18.00   1.00    1.00    --  -40.98 156.00  87.00   95
  4  \w    -69.00  32.00   1.00    1.00    --  -40.98  57.00  90.00  101
  5  \w   -117.00  -8.00   1.00    1.00    --  -40.98 -77.00 -90.00  109
  6  \w   -113.00 -13.00   1.00    1.00    --  -40.98 -57.00-150.00  100
  7  \w   -115.00 -17.00   1.00    1.00    --  -40.98 -37.00-150.00   98
  8  \w   -115.00 -17.00   1.00    1.00    --  -40.98 -37.00-180.00   98
  9  \w     17.00 115.00   1.00    1.00    --   40.98  37.00 -90.00   98
 10  \w      8.00 117.00   1.00    1.00    --   40.98  77.00  60.00  109
 11  \w     13.00 113.00   1.00    1.00    --   40.98  57.00 -60.00  100
 12  \w     74.00 178.00   1.00    1.00    --  106.95  77.00-120.00  104
 13  \w     74.00 178.00   1.00    1.00    --  106.95  77.00-150.00  104
 14  \w     74.00 178.00   1.00    1.00    --  106.95  77.00-180.00  104
 15  \w     34.00 121.00   1.00    1.00    --  106.95-125.00 -90.00   87
 16  \w     74.00 178.00   1.00    1.00    --  106.95  77.00 150.00  104
 17  \w     78.00 178.00   1.00    1.00    --  106.95  61.00-120.00  100
 18  \w     78.00 178.00   1.00    1.00    --  106.95  61.00 150.00  100
 19  \w     78.00 113.00   1.00    1.00    --  106.95  61.00 120.00   35
;
_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      -0.1237054000
_diffrn_orient_matrix_UB_12      0.0193128000
_diffrn_orient_matrix_UB_13      -0.0236954000
_diffrn_orient_matrix_UB_21      0.0410316000
_diffrn_orient_matrix_UB_22      0.0097481000
_diffrn_orient_matrix_UB_23      -0.0630105000
_diffrn_orient_matrix_UB_31      -0.0161562000
_diffrn_orient_matrix_UB_32      -0.1237605000
_diffrn_orient_matrix_UB_33      -0.0086278000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            33134
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.675
_diffrn_reflns_theta_min         1.946
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.783
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55535
_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    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             1336
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.359
_refine_diff_density_min         -0.206
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 4107 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.06(4)
_refine_ls_extinction_coef       0.00220(15)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     858
_refine_ls_number_reflns         10880
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0345
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0542P)^2^+1.0835P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0958
_refine_ls_wR_factor_ref         0.0964
_reflns_Friedel_coverage         0.662
_reflns_Friedel_fraction_full    0.736
_reflns_Friedel_fraction_max     0.689
_reflns_number_gt                10674
_reflns_number_total             10880
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00265k2.cif
_cod_data_source_block           myx-b-7
_cod_database_code               1554812
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 97.05
_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:
 C21B(H21B), C8B(H8B), C7(H7), C9B(H9B), C21(H21), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C10B(H10C,H10D)
2.c Aromatic/amide H refined with riding coordinates:
 C24B(H24B), C28(H28), C27B(H27B), C20B(H20B), C25(H25), C5B(H5B), C26B(H26B),
 C5(H5), C3(H3), C2B(H2B), C4B(H4B), C2(H2), C20(H20), C18B(H18B), C19B(H19B),
 C27(H27), C3B(H3B), C16(H16), C4(H4), C16B(H16B), C17B(H17B), C18(H18),
 C17(H17), C19(H19)
2.d Idealised Me refined as rotating group:
 C14B(H14D,H14E,H14F), C33B(H33A,H33B,H33C), C35B(H35D,H35E,H35F), C35(H35A,
 H35B,H35C), C34B(H34D,H34E,H34F), C34(H34A,H34B,H34C), C30B(H30A,H30B,H30C),
 C14(H14A,H14B,H14C), C36(H36A,H36B,H36C), C31(H31A,H31B,H31C)
;
_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 1.614
_oxdiff_exptl_absorpt_empirical_full_min 0.536