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_1554741
_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         '0.5(C40 H37 N4 O9), 0.5(C40 H38 N4 O9)'
_chemical_formula_sum            'C40 H37.5 N4 O9'
_chemical_formula_weight         718.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_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
;
2019-01-17 deposited with the CCDC.	2019-03-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.6650(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   29.1304(3)
_cell_length_b                   17.26870(10)
_cell_length_c                   17.73280(10)
_cell_measurement_reflns_used    30077
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4910
_cell_measurement_theta_min      2.5300
_cell_volume                     8667.88(12)
_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 0.985
_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    -96.00  -2.00   1.00    1.00    --  -41.11 125.00  90.00   94
  2  \w    -96.00  -2.00   1.00    1.00    --  -41.11 125.00 -60.00   94
  3  \w   -117.00 -51.00   1.00    1.00    --  -41.11-158.00 154.00   66
  4  \w   -117.00  -9.00   1.00    1.00    --  -41.11 -77.00-180.00  108
  5  \w      1.00  82.00   1.00    1.00    --   41.11 -99.00  90.00   81
  6  \w     13.00 113.00   1.00    1.00    --   41.11  57.00  60.00  100
  7  \w     34.00 121.00   1.00    5.00    --  106.95-125.00 -90.00   87
  8  \w     31.00 135.00   1.00    5.00    --  106.95 -30.00 -90.00  104
  9  \w     78.00 178.00   1.00    5.00    --  106.95  61.00  30.00  100
 10  \w     81.00 178.00   1.00    5.00    --  106.95  45.00  90.00   97
 11  \w     35.00 136.00   1.00    5.00    --  106.95 -61.00  90.00  101
 12  \w     79.00 178.00   1.00    5.00    --  106.95  30.00-180.00   99
 13  \w     24.00 109.00   1.00    5.00    --  106.95 -94.00 -60.00   85
 14  \w     34.00 121.00   1.00    5.00    --  106.95-125.00-180.00   87
 15  \w     81.00 178.00   1.00    5.00    --  106.95  45.00-120.00   97
 16  \w     34.00 121.00   1.00    5.00    --  106.95-125.00   0.00   87
 17  \w     94.00 144.00   1.00    5.00    --  106.95 125.00   0.00   50
;
_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      0.0532576000
_diffrn_orient_matrix_UB_12      0.0173925000
_diffrn_orient_matrix_UB_13      0.0264399000
_diffrn_orient_matrix_UB_21      -0.0085487000
_diffrn_orient_matrix_UB_22      0.0815672000
_diffrn_orient_matrix_UB_23      -0.0357677000
_diffrn_orient_matrix_UB_31      -0.0072836000
_diffrn_orient_matrix_UB_32      0.0317031000
_diffrn_orient_matrix_UB_33      0.0775383000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            39695
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.586
_diffrn_reflns_theta_min         2.564
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.651
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70054
_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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             3020
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.568
_refine_diff_density_min         -0.347
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 7297 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     969
_refine_ls_number_reflns         16671
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0509
_refine_ls_R_factor_gt           0.0499
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0990P)^2^+4.0420P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1465
_refine_ls_wR_factor_ref         0.1481
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.963
_reflns_Friedel_fraction_max     0.917
_reflns_number_gt                16246
_reflns_number_total             16671
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9qo00127a2.cif
_cod_data_source_block           myy_19
_cod_original_formula_sum        'C40 H37.50 N4 O9'
_cod_database_code               1554741
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.914
_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
 C02I, C032
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C02I \\sim C032: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
4.a Ternary CH refined with riding coordinates:
 C17(H17), C18(H18), C01H(H01H), C19(H19), C01J(H01J), C02G(H02G)
4.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C01U(H01A,H01B), C02N(H02A,H02C)
4.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C11(H11), C13(H13), C26(H26), C3(H3), C01G(H01G), C14(H14),
 C01Q(H01Q), C01S(H01S), C01W(H01W), C01Y(H01Y), C020(H020), C021(H021), C5(H5),
  C02B(H02B), C4(H4), C24(H24), C02E(H02E), C02F(H02F), C23(H23), C32(H32)
4.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C30(H30A,H30B,H30C), C34(H34A,H34B,
 H34C), C37(H37A,H37B,H37C), C02Q(H02D,H02H,H02I), C02R(H02J,H02K,H02L),
 C02T(H02M,H02N,H02O), C31(H31A,H31B,H31C), C02V(H02P,H02Q,H02R), C02X(H02S,
 H02T,H02U), C02Y(H02V,H02W,H02X), C032(H03A,H03B,H03C), C33(H33A,H33B,H33C)
;
_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 1.505
_oxdiff_exptl_absorpt_empirical_full_min 0.678