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_7127793
_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 unk
_chemical_formula_moiety         'C26 H19 F2 O2 P, C3 H6 O'
_chemical_formula_sum            'C29 H25 F2 O3 P'
_chemical_formula_weight         490.46
_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             2020-07-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.16 svn.r6f6c53a7 for OlexSys, GUI svn.r6139)
;
_audit_update_record
;
2020-09-30 deposited with the CCDC.	2020-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.455(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.0306(3)
_cell_length_b                   9.5877(2)
_cell_length_c                   14.0740(4)
_cell_measurement_reflns_used    3288
_cell_measurement_temperature    292.31(10)
_cell_measurement_theta_max      69.6870
_cell_measurement_theta_min      10.3570
_cell_volume                     1276.22(6)
_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      air
_diffrn_ambient_temperature      292.31(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.982
_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    -12.00  15.00   1.00    1.00    --   54.00 -57.00   0.00   27
  2  \w     37.00  73.00   1.00    1.00    --   54.00 -57.00   0.00   36
  3  \w     51.00  84.00   1.00    1.00    --   54.00 -99.00   0.00   33
  4  \w     56.00 114.00   1.00    1.00    --  108.00-111.00  90.00   58
  5  \w     50.00 106.00   1.00    1.00    --  108.00-111.00   0.00   56
  6  \w     40.00 118.00   1.00    1.00    --  108.00 -50.00 120.00   78
  7  \w     89.00 159.00   1.00    1.00    --  108.00  63.00  60.00   70
  8  \w     88.00 150.00   1.00    1.00    --  108.00  63.00   0.00   62
  9  \w    101.00 160.00   1.00    1.00    --  108.00 111.00 -90.00   59
 10  \w     36.00 128.00   1.00    1.00    --  108.00 -38.00-150.00   92
 11  \w     31.00 117.00   1.00    1.00    --   54.00  77.00 -60.00   86
 12  \w     18.00  52.00   1.00    1.00    --    0.00  57.00-150.00   34
 13  \w    -24.00  35.00   1.00    1.00    --    0.00  38.00-180.00   59
 14  \w    -15.00  82.00   1.00    1.00    --   54.00 -77.00-180.00   97
 15  \w     21.00  56.00   1.00    1.00    --    0.00  57.00  30.00   35
 16  \w     -2.00  24.00   1.00    1.00    --    0.00 -84.00 -10.00   26
 17  \w     17.00  73.00   1.00    1.00    --   54.00 -38.00-180.00   56
 18  \w     42.00  80.00   1.00    1.00    --   54.00  57.00 120.00   38
 19  \w     30.00  67.00   1.00    1.00    --   54.00  38.00 120.00   37
 20  \w     32.00 101.00   1.00    1.00    --   54.00  38.00-180.00   69
 21  \w     38.00  91.00   1.00    1.00    --   54.00  77.00-180.00   53
 22  \w     86.00 111.00   1.00    1.00    --   54.00-125.00-180.00   25
 23  \w     56.00  89.00   1.00    1.00    --  108.00 -63.00-120.00   33
 24  \w     36.00  80.00   1.00    1.00    --  108.00 -25.00 -60.00   44
 25  \w     91.00 116.00   1.00    1.00    --  108.00  50.00  30.00   25
;
_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      -0.0937311000
_diffrn_orient_matrix_UB_12      -0.0084177000
_diffrn_orient_matrix_UB_13      0.0670922000
_diffrn_orient_matrix_UB_21      0.1024684000
_diffrn_orient_matrix_UB_22      0.0979461000
_diffrn_orient_matrix_UB_23      0.0771556000
_diffrn_orient_matrix_UB_31      -0.0851260000
_diffrn_orient_matrix_UB_32      0.1270774000
_diffrn_orient_matrix_UB_33      -0.0550114000
_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  0.0248
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6930
_diffrn_reflns_point_group_measured_fraction_full 0.850
_diffrn_reflns_point_group_measured_fraction_max 0.830
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.871
_diffrn_reflns_theta_min         4.675
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.318
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64348
_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    1.276
_exptl_crystal_description       block
_exptl_crystal_F_000             512
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.251
_refine_diff_density_min         -0.184
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1293 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(15)
_refine_ls_extinction_coef       0.0077(8)
_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   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         4006
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.0395
_refine_ls_R_factor_gt           0.0355
_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^)+(0.0550P)^2^+0.0239P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0976
_reflns_Friedel_coverage         0.588
_reflns_Friedel_fraction_full    0.681
_reflns_Friedel_fraction_max     0.657
_reflns_number_gt                3687
_reflns_number_total             4006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07770d2.cif
_cod_data_source_block           xieshl_0720
_cod_depositor_comments
'Adding full bibliography for 7127787--7127794.cif.'
_cod_original_cell_volume        1276.22(7)
_cod_database_code               7127793
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.913
_reflns_odcompleteness_completeness 99.92
_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 Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C22(H22), C23(H23),
  C24(H24), C25(H25), C26(H26)
2.b Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_shelx_res_checksum              46397
_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 1.631
_oxdiff_exptl_absorpt_empirical_full_min 0.617