Access to P-stereogenic compounds via desymmetrizing enantioselective bromination
Huang, Qiu-Hong; Zhou, Qian-Yi; Yang, Chen; Chen, Li; Cheng, Jin-Pei; Li, Xin; Chemical Science 12 (2021) 4582–4587; doi:10.1039/D0SC07008D

data_1560501
_publ_section_title
;
 Access to P-stereogenic compounds via desymmetrizing enantioselective
 bromination
;
_journal_issue                   12
_journal_name_full               'Chemical Science'
_journal_page_first              4582
_journal_page_last               4587
_journal_paper_doi               10.1039/D0SC07008D
_journal_volume                  12
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H36 Br O3 P'
_chemical_formula_sum            'C28 H36 Br O3 P'
_chemical_formula_weight         531.45
_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     direct
_audit_creation_date             2020-10-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-28 deposited with the CCDC.	2021-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.15691(7)
_cell_length_b                   16.71291(19)
_cell_length_c                   17.53844(17)
_cell_measurement_reflns_used    13445
_cell_measurement_temperature    294.15
_cell_measurement_theta_max      78.8840
_cell_measurement_theta_min      5.0310
_cell_volume                     2684.06(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      294.15
_diffrn_detector                 'CCD plate'
_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    -84.00  39.00   0.50    0.50    --    5.00 -32.00 -32.00  246
  2  \w    -29.00  94.00   0.50    0.50    --    5.00  32.00 127.00  246
  3  \w   -139.00 -15.00   0.50    0.50    --  -49.60 -32.00 -32.00  248
  4  \w   -166.00-114.00   0.50    2.00    -- -110.00 -32.00 -32.00  104
  5  \w   -107.00 -82.00   0.50    2.00    -- -110.00  32.00 127.00   50
  6  \w    -80.00  40.00   0.50    0.50    --  -49.60  38.00-120.00  240
  7  \w    -57.00 -20.00   0.50    0.50    --  -49.60 -57.00-180.00   74
  8  \w    -99.00 -60.00   0.50    0.50    --  -49.60 -57.00-180.00   78
  9  \w   -154.00 -81.00   0.50    2.00    -- -110.00 -57.00 -30.00  146
 10  \w    -80.00 -52.00   0.50    2.00    -- -110.00  38.00   0.00   56
 11  \w   -118.00 -46.00   0.50    2.00    -- -110.00  72.00 -90.00  144
 12  \w   -129.00 -91.00   0.50    2.00    -- -110.00 -57.00  60.00   76
 13  \w   -196.00-136.00   0.50    2.00    -- -110.00 -57.00  60.00  120
 14  \w   -115.00 -89.00   0.50    2.00    -- -110.00  38.00   0.00   52
 15  \w   -139.00 -24.00   0.50    2.00    -- -110.00  57.00  90.00  230
 16  \w   -138.00 -38.00   0.50    2.00    -- -110.00  57.00 -30.00  200
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RCD3): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1120509000
_diffrn_orient_matrix_UB_12      0.0638006000
_diffrn_orient_matrix_UB_13      -0.0246247000
_diffrn_orient_matrix_UB_21      -0.1049749000
_diffrn_orient_matrix_UB_22      -0.0665590000
_diffrn_orient_matrix_UB_23      -0.0264323000
_diffrn_orient_matrix_UB_31      -0.0688394000
_diffrn_orient_matrix_UB_32      -0.0023536000
_diffrn_orient_matrix_UB_33      0.0799981000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            19439
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.270
_diffrn_reflns_theta_min         3.653
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.851
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.315
_exptl_crystal_description       block
_exptl_crystal_F_000             1112
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.457
_refine_diff_density_min         -0.189
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2030 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.031(12)
_refine_ls_extinction_coef       0.00050(16)
_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   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     315
_refine_ls_number_reflns         5564
_refine_ls_number_restraints     12
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0398
_refine_ls_R_factor_gt           0.0381
_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^)+(0.0568P)^2^+0.5219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1076
_refine_ls_wR_factor_ref         0.1094
_reflns_Friedel_coverage         0.718
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                5215
_reflns_number_total             5564
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc07008d2.cif
_cod_data_source_block           p20201015a1
_cod_depositor_comments          'Adding full bibliography for 1560501.cif.'
_cod_database_code               1560501
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.691
_shelx_estimated_absorpt_t_min   0.628
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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, All O(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(Br1) \\sim Ueq, Uanis(Br1A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Sof(H22)=Sof(Br1A)=1-FVAR(1)
 Sof(H13)=Sof(Br1)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C3(H3A), C5(H5), C8(H8), C17(H17), C26(H26)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B), C10(H10A,H10B)
4.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C16(H16), C22(H22), C23(H23), C25(H25)
4.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C27(H27A,H27B,H27C), C28(H28A,H28B,
 H28C)
4.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3)
;
_shelx_res_checksum              91180
_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 1.724
_oxdiff_exptl_absorpt_empirical_full_min 0.738