Construction of 4-hydroxycoumarin derivatives with adjacent quaternary and tertiary stereocenters <i>via</i> ternary catalysis.
Zhang, Mengchu; Zhang, Tianyuan; Yu, Sifan; Qiu, Huang; Yusuf, Abdulla; Xu, Xinfang; Qian, Yu; Hu, Wenhao; Chemical science 14 (2023) 11850–11857; doi:10.1039/d3sc03452f

data_1570132
_publ_section_title
;
 Construction of 4-hydroxycoumarin derivatives with adjacent quaternary
 and tertiary stereocenters <i>via</i> ternary catalysis.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              11850
_journal_page_last               11857
_journal_paper_doi               10.1039/d3sc03452f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C34 H25 Br O6'
_chemical_formula_sum            'C34 H25 Br O6'
_chemical_formula_weight         609.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-14
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-14 deposited with the CCDC.	2023-09-25 downloaded from the CCDC.
;
_cell_angle_alpha                66.991(2)
_cell_angle_beta                 86.552(2)
_cell_angle_gamma                87.993(2)
_cell_formula_units_Z            4
_cell_length_a                   8.6733(3)
_cell_length_b                   17.8722(4)
_cell_length_c                   19.6955(5)
_cell_measurement_reflns_used    18927
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.3150
_cell_measurement_theta_min      2.4260
_cell_volume                     2804.82(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     70.00 107.00   0.50    0.22    --  105.85 -77.00-120.00   74
  2  \w     82.00 107.00   0.50    0.22    --  105.85 -77.00   0.00   50
  3  \w     33.00  62.00   0.50    0.22    --  105.85 -77.00   0.00   58
  4  \w     47.00  73.00   0.50    0.22    --  105.85 -61.00 150.00   52
  5  \w     33.00  81.00   0.50    0.22    --  105.85 -77.00 120.00   96
  6  \w     42.00  67.00   0.50    0.22    --  105.85 -61.00  60.00   50
  7  \w     -6.00  19.00   0.50    0.06    --   44.84 -27.00  68.00   50
  8  \w     33.00  70.00   0.50    0.22    --  105.85 -61.00-120.00   74
  9  \w     42.00  72.00   0.50    0.22    --  105.85 -61.00-150.00   60
 10  \w     20.00  72.00   0.50    0.06    --   44.84-125.00 -60.00  104
 11  \w     54.00  94.00   0.50    0.06    --   44.84-125.00 -30.00   80
 12  \w     58.00 112.00   0.50    0.22    --  105.85-125.00  90.00  108
 13  \w     68.00 112.00   0.50    0.22    --  105.85-125.00 150.00   88
 14  \w     80.00 112.00   0.50    0.22    --  105.85-125.00 -90.00   64
 15  \w     57.00 111.00   0.50    0.22    --  105.85-125.00-120.00  108
 16  \w     37.00  78.00   0.50    0.22    --  105.85-125.00-150.00   82
 17  \w     83.00 108.00   0.50    0.22    --  105.85-125.00-150.00   50
 18  \w     33.00 104.00   0.50    0.22    --  105.85 -94.00-120.00  142
 19  \w     45.00 105.00   0.50    0.22    --  105.85 -94.00 -30.00  120
 20  \w     87.00 112.00   0.50    0.22    --  105.85-125.00  30.00   50
 21  \w     35.00  93.00   0.50    0.22    --  105.85 -94.00  30.00  116
 22  \w     49.00 121.00   0.50    0.06    --   44.84  27.00-129.00  144
 23  \w     98.00 167.00   0.50    0.22    --  105.85  30.00-180.00  138
 24  \w     96.00 177.00   0.50    0.22    --  105.85  27.00-129.00  162
 25  \w     88.00 175.00   0.50    0.22    --  105.85  61.00 -90.00  174
 26  \w     88.00 138.00   0.50    0.22    --  105.85  61.00 -60.00  100
 27  \w    -23.00  18.00   0.50    0.06    --  -44.84  19.00  30.00   82
 28  \w    -23.00  33.00   0.50    0.06    --  -44.84  19.00-180.00  112
 29  \w    -30.00  31.00   0.50    0.06    --  -44.84  27.00-129.00  122
 30  \w    -18.00   8.00   0.50    0.06    --  -44.84  19.00 -30.00   52
 31  \w    -66.00 -36.00   0.50    0.06    --  -44.84  77.00  90.00   60
 32  \w    -61.00 -35.00   0.50    0.22    -- -100.00  61.00  60.00   52
 33  \w    -54.00 -29.00   0.50    0.22    -- -100.00 125.00 120.00   50
 34  \w   -103.00 -77.00   0.50    0.22    -- -100.00 125.00 120.00   52
 35  \w    -70.00 -29.00   0.50    0.22    -- -100.00 125.00  60.00   82
 36  \w    -62.00 -30.00   0.50    0.22    -- -100.00 125.00 -60.00   64
 37  \w   -107.00 -76.00   0.50    0.22    -- -100.00 125.00 -60.00   62
 38  \w    -69.00 -44.00   0.50    0.22    -- -100.00  61.00 120.00   50
 39  \w   -156.00-127.00   0.50    0.22    -- -100.00 -30.00  30.00   58
 40  \w   -174.00-144.00   0.50    0.22    -- -100.00 -27.00  68.00   60
 41  \w   -117.00 -85.00   0.50    0.22    -- -100.00 -30.00  30.00   64
 42  \w   -123.00 -84.00   0.50    0.22    -- -100.00 -27.00  68.00   78
 43  \w   -121.00 -27.00   0.50    0.06    --  -44.84 -27.00  68.00  188
 44  \w   -103.00 -76.00   0.50    0.22    -- -100.00 -15.00 -60.00   54
 45  \w   -175.00-111.00   0.50    0.22    -- -100.00 -15.00 -60.00  128
;
_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      -0.1604991000
_diffrn_orient_matrix_UB_12      -0.0380562000
_diffrn_orient_matrix_UB_13      0.0263665000
_diffrn_orient_matrix_UB_21      0.0546478000
_diffrn_orient_matrix_UB_22      -0.0752183000
_diffrn_orient_matrix_UB_23      -0.0151661000
_diffrn_orient_matrix_UB_31      0.0540604000
_diffrn_orient_matrix_UB_32      -0.0408111000
_diffrn_orient_matrix_UB_33      0.0794662000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0537
_diffrn_reflns_av_unetI/netI     0.0518
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            29802
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.597
_diffrn_reflns_theta_max         66.597
_diffrn_reflns_theta_min         2.440
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.381
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48695
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
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    1.443
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.624
_refine_diff_density_min         -1.052
_refine_diff_density_rms         0.151
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         9853
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.0812
_refine_ls_R_factor_gt           0.0746
_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^)+(0.1056P)^2^+16.1041P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2185
_refine_ls_wR_factor_ref         0.2223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8568
_reflns_number_total             9853
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03452f2.cif
_cod_data_source_block           20230504-zmc-0755-3_auto
_cod_depositor_comments
;
Adding full bibliography for 1570130--1570133.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C68 H50 Br2 O12'
_cod_original_formula_weight         1218.90
_cod_original_formula_moiety         '2(C34 H25 Br O6)'
_cod_original_formula_units_Z            2
_cod_database_code               1570132
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O'
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.717
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.713229
 0.286771
2. 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, All O(H) groups
3.a Ternary CH refined with riding coordinates:
 C17(H17), C44(H44)
3.b Secondary CH2 refined with riding coordinates:
 C62(H62a,H62b), C7(H7a,H7b)
3.c Aromatic/amide H refined with riding coordinates:
 C39(H39), C14(H14), C13(H13), C61(H61), C12(H12), C35(H35), C38(H38),
 C10(H10), C37(H37), C21(H21), C48(H48), C59(H59), C65(H65), C22(H22), C11(H11),
  C36(H36), C58(H58), C24(H24), C1(H1a), C4(H4), C60(H60), C64(H64), C34(H34),
 C50(H50), C2(H2), C51(H51), C57(H57), C30(H30), C49(H49), C5(H5), C23(H23),
 C33(H33), C31(H31), C67(H67), C68(H68), C32(H32)
3.d Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C43(H43a,H43b,H43c)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O9(H9)
;
_shelx_res_checksum              14081
_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 2.740
_oxdiff_exptl_absorpt_empirical_full_min 0.290