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_7127794
_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         'C18 H18 F O2 P'
_chemical_formula_sum            'C18 H18 F O2 P'
_chemical_formula_weight         316.29
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-08-19
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2020-09-30 deposited with the CCDC.	2020-12-24 downloaded from the CCDC.
;
_cell_angle_alpha                81.880(6)
_cell_angle_beta                 81.526(6)
_cell_angle_gamma                66.712(8)
_cell_formula_units_Z            2
_cell_length_a                   8.0210(6)
_cell_length_b                   9.7257(8)
_cell_length_c                   11.0936(8)
_cell_measurement_reflns_used    4044
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.8520
_cell_measurement_theta_min      4.9220
_cell_volume                     782.94(11)
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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     30.00  78.00   1.00    2.00    --   54.00 -77.00  90.00   48
  2  \w     48.00  91.00   1.00    2.00    --   54.00 -23.00  42.00   43
  3  \w     78.00 146.00   1.00    4.00    --  108.00 -91.00  90.00   68
  4  \w     62.00 115.00   1.00    4.00    --  108.00-111.00 -90.00   53
  5  \w     93.00 145.00   1.00    4.00    --  108.00 -91.00 -90.00   52
  6  \w    104.00 176.00   1.00    4.00    --  108.00  38.00-150.00   72
  7  \w    100.00 149.00   1.00    4.00    --  108.00 111.00 -30.00   49
  8  \w     96.00 159.00   1.00    4.00    --  108.00  38.00 -30.00   63
  9  \w     94.00 122.00   1.00    2.00    --   54.00  57.00-120.00   28
 10  \w     79.00 164.00   1.00    4.00    --  108.00  77.00 -90.00   85
 11  \w     86.00 177.00   1.00    4.00    --  108.00  50.00-120.00   91
 12  \w     55.00 126.00   1.00    4.00    --  108.00 -38.00 -90.00   71
 13  \w     51.00 128.00   1.00    4.00    --  108.00 -50.00  60.00   77
 14  \w     37.00 103.00   1.00    4.00    --  108.00-111.00  90.00   66
 15  \w     36.00  63.00   1.00    4.00    --  108.00 -91.00  90.00   27
 16  \w     -2.00  45.00   1.00    2.00    --   54.00 -23.00  42.00   47
 17  \w    -13.00  22.00   1.00    1.00    --    0.00  57.00  30.00   35
 18  \w    -13.00  37.00   1.00    2.00    --   54.00 -57.00 -90.00   50
 19  \w      7.00  80.00   1.00    2.00    --   54.00 -99.00 -90.00   73
 20  \w     43.00 125.00   1.00    4.00    --  108.00 -63.00-150.00   82
 21  \w     38.00 123.00   1.00    2.00    --   54.00  57.00-150.00   85
 22  \w     42.00  69.00   1.00    1.00    --    0.00  57.00  30.00   27
 23  \w    -19.00  20.00   1.00    1.00    --    0.00 -57.00-120.00   39
 24  \w    -16.00  81.00   1.00    2.00    --   54.00 -77.00   0.00   97
 25  \w    -63.00 -37.00   1.00    1.00    --    0.00 -57.00-120.00   26
 26  \w     19.00  45.00   1.00    1.00    --    0.00  57.00-120.00   26
 27  \w    -25.00   7.00   1.00    1.00    --    0.00  19.00-180.00   32
 28  \w     34.00  60.00   1.00    1.00    --    0.00  19.00-180.00   26
 29  \w    -17.00   9.00   1.00    1.00    --    0.00  57.00-120.00   26
 30  \w    -18.00   9.00   1.00    1.00    --   24.00 106.00 179.94   27
 31  \w     -2.00  23.00   1.00    2.00    --   36.00  92.00   8.71   25
 32  \w     -6.00  19.00   1.00    2.00    --   36.00  99.00 -95.83   25
 33  \w      2.00  27.00   1.00    2.00    --   40.00  92.00-173.00   25
 34  \w     12.00  37.00   1.00    2.00    --   44.00  81.00 117.43   25
 35  \w     16.00  41.00   1.00    2.00    --   48.00  80.00   0.36   25
 36  \w     20.00  45.00   1.00    2.00    --   52.00  80.00 102.29   25
 37  \w     21.00  46.00   1.00    2.00    --   52.00  79.00 156.41   25
 38  \w     90.00 116.00   1.00    2.00    --   54.00  77.00  60.00   26
 39  \w     24.00  67.00   1.00    2.00    --   54.00  77.00  60.00   43
 40  \w     25.00  51.00   1.00    2.00    --   54.00  77.00 -60.00   26
 41  \w     26.00  52.00   1.00    2.00    --   54.00  77.00-120.00   26
 42  \w     42.00  73.00   1.00    2.00    --   54.00 -57.00 120.00   31
 43  \w     30.00  62.00   1.00    2.00    --   56.00  75.00-154.85   32
 44  \w     99.00 125.00   1.00    2.00    --   60.00  57.00 117.55   26
 45  \w    104.00 129.00   1.00    2.00    --   60.00  71.00 -27.26   25
 46  \w     34.00  72.00   1.00    2.00    --   60.00  71.00 -27.26   38
 47  \w     40.00  65.00   1.00    2.00    --   60.00  57.00 117.55   25
 48  \w     34.00  60.00   1.00    2.00    --   60.00  70.00 -96.81   26
 49  \w     40.00  74.00   1.00    2.00    --   64.00  71.00  19.87   34
 50  \w     78.00 127.00   1.00    2.00    --   64.00  71.00  19.87   49
 51  \w     42.00  69.00   1.00    2.00    --   64.00  62.00 122.77   27
 52  \w     48.00  79.00   1.00    2.00    --   68.00  61.00 -49.85   31
 53  \w     48.00  87.00   1.00    2.00    --   68.00  53.00-160.59   39
 54  \w     45.00  71.00   1.00    2.00    --   68.00  47.00  38.82   26
 55  \w     41.00  71.00   1.00    2.00    --   68.00  74.00 130.68   30
 56  \w     50.00  76.00   1.00    2.00    --   72.00  66.00 -99.44   26
 57  \w     55.00 100.00   1.00    2.00    --   76.00  62.00 160.70   45
 58  \w     59.00  89.00   1.00    2.00    --   80.00  46.00 145.00   30
 59  \w     78.00 104.00   1.00    4.00    --  108.00  77.00 -30.00   26
 60  \w     83.00 110.00   1.00    4.00    --  108.00  38.00  30.00   27
 61  \w     79.00 105.00   1.00    4.00    --  108.00  77.00-180.00   26
;
_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      0.1729671000
_diffrn_orient_matrix_UB_12      0.0363687000
_diffrn_orient_matrix_UB_13      -0.0219499000
_diffrn_orient_matrix_UB_21      0.1169857000
_diffrn_orient_matrix_UB_22      -0.1662954000
_diffrn_orient_matrix_UB_23      0.0344374000
_diffrn_orient_matrix_UB_31      0.0238178000
_diffrn_orient_matrix_UB_32      -0.0318253000
_diffrn_orient_matrix_UB_33      -0.1349472000
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            7365
_diffrn_reflns_point_group_measured_fraction_full 0.768
_diffrn_reflns_point_group_measured_fraction_max 0.768
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         4.046
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.690
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32615
_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    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             332
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1286 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     349
_refine_ls_number_reflns         4258
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0573
_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^)+(0.1069P)^2^+0.4491P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1652
_refine_ls_wR_factor_ref         0.1694
_reflns_Friedel_coverage         0.542
_reflns_Friedel_fraction_full    0.540
_reflns_Friedel_fraction_max     0.540
_reflns_number_gt                3984
_reflns_number_total             4258
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0cc07770d2.cif
_cod_data_source_block           xieshl_190_392_2
_cod_depositor_comments
'Adding full bibliography for 7127787--7127794.cif.'
_cod_database_code               7127794
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.935
_shelx_estimated_absorpt_t_min   0.836
_reflns_odcompleteness_completeness 99.71
_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
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C4(H4A,H4B), C23(H23A,H23B), C21(H21A,
 H21B), C22(H22A,H22B), C24(H24A,H24B)
2.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C18(H18), C17(H17),
 C16(H16), C15(H15), C26(H26), C27(H27), C29(H29), C28(H28), C30(H30), C32(H32),
  C33(H33), C34(H34), C35(H35), C36(H36)
2.c Fitted hexagon refined as free rotating group:
 C7(C8,C9,C10,C11,C12), C13(C18,C17,C16,C15,C14), C25(C26,C27,C29,C28,C30),
 C32(C33,C34,C35,C36,C31)
;
_shelx_res_checksum              95503
_olex2_date_sample_data_collection 2020-08-16
_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 3.014
_oxdiff_exptl_absorpt_empirical_full_min 0.477