The organocatalytic enantiodivergent fluorination of β-ketodiaryl-phosphine oxides for the construction of carbon-fluorine quaternary stereocenters.
Xie, Shaolei; He, Zhi-Juan; Zhang, Ling-Hui; Huang, Bo-Lun; Chen, Xiao-Wei; Zhan, Zong-Song; Zhang, Fu-Min; Chemical communications (Cambridge, England) 57 (2021) 2069–2072; doi:10.1039/d0cc07770d

data_7127788
_publ_section_title
;
 The organocatalytic enantiodivergent fluorination of
 \b-ketodiaryl-phosphine oxides for the construction of carbon-fluorine
 quaternary stereocenters.
;
_journal_issue                   16
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              2069
_journal_page_last               2072
_journal_paper_doi               10.1039/d0cc07770d
_journal_volume                  57
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C H Cl3, C27 H22 F O2 P'
_chemical_formula_sum            'C28 H23 Cl3 F O2 P'
_chemical_formula_weight         547.78
_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             2020-07-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_audit_update_record
;
2020-09-30 deposited with the CCDC.	2020-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.935(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.9203(2)
_cell_length_b                   9.7787(2)
_cell_length_c                   13.8908(3)
_cell_measurement_reflns_used    6001
_cell_measurement_temperature    172.90(10)
_cell_measurement_theta_max      69.8150
_cell_measurement_theta_min      9.6150
_cell_volume                     1307.86(5)
_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 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.90(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     36.00 110.00   1.00    1.00    --   54.00  57.00  60.00   74
  2  \w     87.00 115.00   1.00    1.00    --  108.00  50.00 -30.00   28
  3  \w    118.00 178.00   1.00    1.00    --  108.00  77.00 -60.00   60
  4  \w    146.00 172.00   1.00    1.00    --  108.00  44.00 -94.54   26
  5  \w    148.00 174.00   1.00    1.00    --  108.00  50.00-150.00   26
  6  \w    121.00 177.00   1.00    1.00    --  108.00  77.00-180.00   56
  7  \w    140.00 178.00   1.00    1.00    --  108.00  50.00 -30.00   38
  8  \w     96.00 122.00   1.00    1.00    --  108.00  50.00-120.00   26
  9  \w     87.00 113.00   1.00    1.00    --  108.00  50.00 -60.00   26
 10  \w     86.00 112.00   1.00    1.00    --  108.00  63.00 -60.00   26
 11  \w     84.00 110.00   1.00    1.00    --  108.00  38.00 -60.00   26
 12  \w     86.00 112.00   1.00    1.00    --  108.00  63.00 -30.00   26
 13  \w     78.00 103.00   1.00    1.00    --  108.00  77.00 -60.00   25
 14  \w     82.00 112.00   1.00    1.00    --  108.00  38.00 -30.00   30
 15  \w     82.00 176.00   1.00    1.00    --  108.00  38.00   0.00   94
 16  \w     87.00 113.00   1.00    1.00    --  108.00  50.00-150.00   26
 17  \w     89.00 150.00   1.00    1.00    --  108.00  63.00-120.00   61
 18  \w     83.00 113.00   1.00    1.00    --  108.00  69.00-152.78   30
 19  \w     79.00 105.00   1.00    1.00    --  108.00  77.00-120.00   26
 20  \w     84.00 110.00   1.00    1.00    --  108.00  38.00 -90.00   26
 21  \w     83.00 108.00   1.00    1.00    --  108.00  38.00-120.00   25
 22  \w     80.00 106.00   1.00    1.00    --  108.00  77.00-150.00   26
 23  \w     79.00 177.00   1.00    1.00    --  108.00  75.00-101.76   98
 24  \w     85.00 111.00   1.00    1.00    --  108.00  44.00 -94.54   26
 25  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 -90.00   26
 26  \w     78.00 104.00   1.00    1.00    --  108.00  77.00 -30.00   26
 27  \w     77.00 109.00   1.00    1.00    --  108.00  25.00 -90.00   32
 28  \w     55.00 136.00   1.00    1.00    --  108.00 -25.00-180.00   81
 29  \w     76.00 102.00   1.00    1.00    --  108.00-111.00-120.00   26
 30  \w     57.00 129.00   1.00    1.00    --  108.00 -63.00-150.00   72
 31  \w     44.00  70.00   1.00    1.00    --  108.00-111.00-120.00   26
 32  \w     23.00  65.00   1.00    1.00    --   54.00 -38.00-150.00   42
 33  \w     41.00  68.00   1.00    1.00    --    0.00   0.00 -60.00   27
 34  \w     32.00 118.00   1.00    1.00    --   54.00  19.00  30.00   86
 35  \w     54.00  86.00   1.00    1.00    --   54.00  77.00 -60.00   32
 36  \w     32.00  98.00   1.00    1.00    --   54.00  77.00 -90.00   66
 37  \w     29.00  54.00   1.00    1.00    --    0.00  77.00   0.00   25
 38  \w     24.00  57.00   1.00    1.00    --   54.00  77.00-120.00   33
 39  \w     65.00 115.00   1.00    1.00    --  108.00 178.00 -30.00   50
 40  \w    -20.00  12.00   1.00    1.00    --    0.00  77.00   0.00   32
 41  \w    -10.00  69.00   1.00    1.00    --   54.00 -57.00  90.00   79
 42  \w     36.00  78.00   1.00    1.00    --  108.00-111.00 120.00   42
 43  \w    -55.00  -7.00   1.00    1.00    --    0.00 -57.00 -30.00   48
 44  \w     -5.00  71.00   1.00    1.00    --   54.00 -57.00-180.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1586424000
_diffrn_orient_matrix_UB_12      0.0062077000
_diffrn_orient_matrix_UB_13      -0.0137028000
_diffrn_orient_matrix_UB_21      0.0153066000
_diffrn_orient_matrix_UB_22      -0.0647216000
_diffrn_orient_matrix_UB_23      0.1031376000
_diffrn_orient_matrix_UB_31      0.0139304000
_diffrn_orient_matrix_UB_32      0.1435442000
_diffrn_orient_matrix_UB_33      0.0472349000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0386
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            10492
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        66.582
_diffrn_reflns_theta_max         66.582
_diffrn_reflns_theta_min         4.592
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.012
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44062
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.391
_exptl_crystal_description       block
_exptl_crystal_F_000             564
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.335
_refine_diff_density_min         -0.435
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 1854 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     317
_refine_ls_number_reflns         4451
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0414
_refine_ls_R_factor_gt           0.0404
_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^)+(0.0656P)^2^+0.5059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1077
_refine_ls_wR_factor_ref         0.1089
_reflns_Friedel_coverage         0.809
_reflns_Friedel_fraction_full    0.919
_reflns_Friedel_fraction_max     0.919
_reflns_number_gt                4335
_reflns_number_total             4451
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07770d2.cif
_cod_data_source_block           xieshl_0715
_cod_depositor_comments
'Adding full bibliography for 7127787--7127794.cif.'
_cod_original_cell_volume        1307.85(5)
_cod_database_code               7127788
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C28(H28)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              96470
_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 3.041
_oxdiff_exptl_absorpt_empirical_full_min 0.544