Bifunctional oxindole-chromone 4C building block directed asymmetric synthesis of bispirocyclic hexahydroxanthones featuring five contiguous stereocenters and two side-by-side oxindoles
Liu, Xiong-Li; Gong, Yi; Chen, Shuang; Zuo, Xiong; Yao, Zhen; Zhou, Ying; Organic Chemistry Frontiers 6 (2019) 1603–; doi:10.1039/C9QO00127A

data_1554740
_publ_section_title
;
 Bifunctional oxindole-chromone 4C building block directed asymmetric
 synthesis of bispirocyclic hexahydroxanthones featuring five contiguous
 stereocenters and two side-by-side oxindoles
;
_journal_issue                   10
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              1603
_journal_paper_doi               10.1039/C9QO00127A
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C43 H36 N4 O9'
_chemical_formula_sum            'C43 H36 N4 O9'
_chemical_formula_weight         752.76
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-08-17 deposited with the CCDC.	2019-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.41181(11)
_cell_length_b                   27.64710(16)
_cell_length_c                   17.61491(11)
_cell_measurement_reflns_used    46989
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.3980
_cell_measurement_theta_min      2.9670
_cell_volume                     8479.57(9)
_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 2014/5 (Sheldrick, 2014)'
_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 0.998
_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   -116.00 -17.00   1.00    1.00    --  -41.11 -37.00-120.00   99
  2  \w      1.00  82.00   1.00    1.00    --   41.11 -99.00  90.00   81
  3  \w     23.00  97.00   1.00    1.00    --   41.11-125.00  90.00   74
  4  \w      1.00  82.00   1.00    1.00    --   41.11 -99.00 -90.00   81
  5  \w     24.00 109.00   1.00    4.00    --  106.95 -94.00 150.00   85
  6  \w     35.00 136.00   1.00    4.00    --  106.95 -61.00-150.00  101
  7  \w     24.00 109.00   1.00    4.00    --  106.95 -94.00 120.00   85
  8  \w     94.00 178.00   1.00    4.00    --  106.95 125.00 120.00   84
  9  \w     78.00 178.00   1.00    4.00    --  106.95  61.00   0.00  100
 10  \w     79.00 178.00   1.00    4.00    --  106.95  30.00-120.00   99
 11  \w     34.00 121.00   1.00    4.00    --  106.95-125.00 120.00   87
 12  \w   -117.00  -9.00   1.00    1.00    --  -41.11 -77.00-150.00  108
 13  \w   -113.00 -13.00   1.00    1.00    --  -41.11 -57.00   0.00  100
 14  \w   -114.00 -11.00   1.00    1.00    --  -41.11 -65.00 118.00  103
 15  \w     79.00 178.00   1.00    4.00    --  106.95  30.00-180.00   99
 16  \w     78.00 178.00   1.00    4.00    --  106.95  61.00 -60.00  100
 17  \w     78.00 178.00   1.00    4.00    --  106.95  59.00 103.00  100
 18  \w     78.00 178.00   1.00    4.00    --  106.95  61.00  30.00  100
 19  \w     77.00 178.00   1.00    4.00    --  106.95  65.00-105.00  101
 20  \w     79.00 178.00   1.00    4.00    --  106.95  30.00  90.00   99
 21  \w    -65.00  33.00   1.00    1.00    --  -41.11  37.00-150.00   98
 22  \w      9.00 117.00   1.00    1.00    --   41.11  77.00  30.00  108
 23  \w      9.00 117.00   1.00    1.00    --   41.11  77.00 120.00  108
 24  \w     78.00 178.00   1.00    4.00    --  106.95  61.00 120.00  100
 25  \w     78.00 178.00   1.00    4.00    --  106.95  61.00-180.00  100
 26  \w     24.00  71.00   1.00    4.00    --  106.95 -94.00-150.00   47
 27  \w     78.00 178.00   1.00    4.00    --  106.95  61.00 -30.00  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      -0.0660979000
_diffrn_orient_matrix_UB_12      0.0175083000
_diffrn_orient_matrix_UB_13      -0.0511986000
_diffrn_orient_matrix_UB_21      -0.0073831000
_diffrn_orient_matrix_UB_22      -0.0511900000
_diffrn_orient_matrix_UB_23      -0.0338001000
_diffrn_orient_matrix_UB_31      -0.0583498000
_diffrn_orient_matrix_UB_32      -0.0134244000
_diffrn_orient_matrix_UB_33      0.0622898000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0140
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            64308
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.539
_diffrn_reflns_theta_min         2.999
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.690
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69701
_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    1.179
_exptl_crystal_description       block
_exptl_crystal_F_000             3152
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.152
_refine_diff_density_min         -0.187
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 3773 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     509
_refine_ls_number_reflns         8531
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0335
_refine_ls_R_factor_gt           0.0331
_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^)+(0.0609P)^2^+1.6420P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0899
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                8396
_reflns_number_total             8531
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00127a2.cif
_cod_data_source_block           exp_1007
_cod_original_cell_volume        8479.58(9)
_cod_database_code               1554740
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.922
_shelx_estimated_absorpt_t_min   0.904
_reflns_odcompleteness_completeness 100.00
_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. Rigid bond restraints
 C36, C37
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C36 \\sim C37: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
4.a Ternary CH refined with riding coordinates:
 C10(H10), C11(H11), C12(H12)
4.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C32(H32A,H32B)
4.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C30(H30), C2(H2), C20(H20), C19(H19), C5(H5), C3(H3), C31(H31),
 C29(H29), C17(H17), C34(H34), C4(H4), C18(H18), C37(H37), C38(H38), C35(H35),
 C36(H36)
4.d Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C42(H42A,H42B,
 H42C)
;
_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 1.348
_oxdiff_exptl_absorpt_empirical_full_min 0.680