P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric P-C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides.
Dai, Qiang; Li, Wenbo; Li, Zhiming; Zhang, Junliang; Journal of the American Chemical Society 141 (2019) 20556–20564; doi:10.1021/jacs.9b11938

data_4133759
_publ_section_title
;
 P-Chiral Phosphines Enabled by Palladium/Xiao-Phos-Catalyzed Asymmetric
 P-C Cross-Coupling of Secondary Phosphine Oxides and Aryl Bromides.
;
_journal_issue                   51
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              20556
_journal_page_last               20564
_journal_paper_doi               10.1021/jacs.9b11938
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C28 H28 O4 P2, 0.5(H2 O)'
_chemical_formula_sum            'C28 H29 O4.5 P2'
_chemical_formula_weight         499.45
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.3811(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.97867(5)
_cell_length_b                   20.51133(8)
_cell_length_c                   13.55182(6)
_cell_measurement_reflns_used    44403
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.1800
_cell_measurement_theta_min      3.9120
_cell_volume                     2495.04(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     23.00  87.00   1.00    1.00    --    0.00  38.00  30.00   64
  2  \w    -89.00  14.00   1.00    1.00    --    0.00 -38.00 -90.00  103
  3  \w    -19.00  21.00   1.00    1.00    --    0.00  38.00  30.00   40
  4  \w    -55.00  23.00   1.00    1.00    --    0.00 -57.00  30.00   78
  5  \w     -3.00  24.00   1.00    1.00    --    0.00 -19.00 120.00   27
  6  \w    -23.00  77.00   1.00    1.00    --    0.00  57.00 -90.00  100
  7  \w    -89.00 -56.00   1.00    1.00    --    0.00 -19.00 120.00   33
  8  \w    -26.00  32.00   1.00    1.00    --    0.00  77.00  30.00   58
  9  \w    -19.00  83.00   1.00    1.00    --    0.00  38.00-150.00  102
 10  \w     44.00  87.00   1.00    1.00    --    0.00  77.00  30.00   43
 11  \w    -32.00  24.00   1.00    1.00    --    0.00  82.00  90.00   56
 12  \w     63.00  92.00   1.00    1.00    --   95.80  81.00  96.60   29
 13  \w     68.00  93.00   1.00    1.00    --   95.80  68.00 179.46   25
 14  \w     64.00  90.00   1.00    1.00    --   95.80  82.00  15.93   26
 15  \w    135.00 161.00   1.00    1.00    --   95.80  75.00 -35.76   26
 16  \w     66.00  92.00   1.00    1.00    --   95.80  75.00 -35.76   26
 17  \w     66.00  91.00   1.00    1.00    --   95.80  74.00  61.64   25
 18  \w     74.00 185.00   1.00    1.00    --   95.80  51.00 144.32  111
 19  \w    154.00 184.00   1.00    1.00    --   95.80  82.00 150.00   30
 20  \w    124.00 160.00   1.00    1.00    --   95.80  55.00-151.00   36
 21  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 150.00   25
 22  \w     30.00 115.00   1.00    1.00    --   95.80 -82.00   0.00   85
 23  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 24  \w     71.00  97.00   1.00    1.00    --   95.80  61.00  30.00   26
 25  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 26  \w     65.00  91.00   1.00    1.00    --   95.80  77.00   0.00   26
 27  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 28  \w    114.00 146.00   1.00    1.00    --   95.80  82.00-180.00   32
 29  \w    158.00 185.00   1.00    1.00    --   95.80  82.00-180.00   27
 30  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -60.00   26
 31  \w     72.00 107.00   1.00    1.00    --   95.80  55.00-151.00   35
 32  \w     66.00 107.00   1.00    1.00    --   95.80  74.00 -65.20   41
 33  \w      6.00 119.00   1.00    1.00    --   95.80 -61.00  90.00  113
 34  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  90.00   25
 35  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-120.00   25
 36  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-149.26   26
 37  \w     70.00 126.00   1.00    1.00    --   95.80  62.00-107.05   56
 38  \w     76.00 182.00   1.00    1.00    --   95.80  45.00-180.00  106
 39  \w     76.00 119.00   1.00    1.00    --   95.80  45.00-120.00   43
 40  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 120.00   26
 41  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 42  \w     95.00 120.00   1.00    1.00    --   95.80  77.00-120.00   25
 43  \w     65.00 176.00   1.00    1.00    --   95.80  77.00 -60.00  111
 44  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 150.00   26
 45  \w      7.00 127.00   1.00    1.00    --   95.80 -82.00  90.00  120
 46  \w     63.00 100.00   1.00    1.00    --   95.80  82.00  30.00   37
 47  \w    112.00 184.00   1.00    1.00    --   95.80  82.00  30.00   72
 48  \w     75.00 123.00   1.00    1.00    --   95.80  45.00  90.00   48
 49  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -90.00   25
 50  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 51  \w     63.00  88.00   1.00    1.00    --   95.80  81.00-108.60   25
 52  \w     80.00 105.00   1.00    1.00    --   95.80 -82.00 150.00   25
 53  \w     76.00 183.00   1.00    1.00    --   95.80  30.00  90.00  107
 54  \w     75.00 167.00   1.00    1.00    --   95.80  45.00 120.00   92
 55  \w     72.00 185.00   1.00    1.00    --   95.80  60.00 -18.27  113
 56  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 57  \w     71.00 102.00   1.00    1.00    --   95.80  61.00   0.00   31
 58  \w     71.00  96.00   1.00    1.00    --   95.80  61.00  90.00   25
 59  \w     11.00 118.00   1.00    1.00    --   95.80 -82.00-120.00  107
 60  \w     65.00 116.00   1.00    1.00    --   95.80 -61.00-120.00   51
 61  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -30.00   26
 62  \w    145.00 171.00   1.00    1.00    --   95.80  82.00  15.93   26
 63  \w    160.00 185.00   1.00    1.00    --   95.80  68.00 179.46   25
 64  \w     69.00 108.00   1.00    1.00    --   95.80  65.00  33.51   39
 65  \w     70.00 175.00   1.00    1.00    --   95.80  62.00 -74.96  105
 66  \w     76.00 115.00   1.00    1.00    --   95.80  37.00  39.07   39
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0191613000
_diffrn_orient_matrix_UB_12      -0.0511684000
_diffrn_orient_matrix_UB_13      0.0825116000
_diffrn_orient_matrix_UB_21      0.0151706000
_diffrn_orient_matrix_UB_22      -0.0539234000
_diffrn_orient_matrix_UB_23      -0.0781855000
_diffrn_orient_matrix_UB_31      0.1699901000
_diffrn_orient_matrix_UB_32      0.0105911000
_diffrn_orient_matrix_UB_33      0.0004496000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0437
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            57946
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.910
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.870
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55714
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
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    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             1052
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.243
_refine_diff_density_min         -0.220
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 4157 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(5)
_refine_ls_extinction_coef       0.00041(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2017/1 (Sheldrick 2017)'
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     630
_refine_ls_number_reflns         8872
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0229
_refine_ls_R_factor_gt           0.0226
_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^)+(0.0285P)^2^+0.6367P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0583
_refine_ls_wR_factor_ref         0.0584
_reflns_Friedel_coverage         0.931
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                8759
_reflns_number_total             8872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11938_si_002.cif
_cod_data_source_block           exp_1020
_cod_depositor_comments
;
Adding full bibliography for 4133759--4133760.cif.

2020-08-12
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_cell_volume        2495.037(19)
_cod_original_formula_moiety     '2(C28 H28 O4 P2), H2 O'
_cod_original_formula_sum        'C56 H58 O9 P4'
_cod_original_formula_units_Z    2
_cod_original_formula_weight     998.90
_cod_database_code               4133759
_shelx_shelxl_version_number     2017/1
_reflns_odcompleteness_completeness 99.93
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2.a Free rotating group:
 O9(H9A,H9B)
2.b Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C15(H15A,H15B), C14(H14A,H14B), C55(H55A,H55B)
2.c Aromatic/amide H refined with riding coordinates:
 C24(H24), C45(H45), C34(H34), C53(H53), C51(H51), C52(H52), C43(H43),
 C32(H32), C27(H27), C50(H50), C37(H37), C30(H30), C36(H36), C47(H47), C3(H3),
 C17(H17), C46(H46), C33(H33), C20(H20), C19(H19), C18(H18), C39(H39), C25(H25),
  C26(H26), C6(H6), C4(H4), C44(H44), C31(H31), C21(H21), C38(H38), C2(H2),
 C11(H11), C10(H10), C8(H8), C5(H5), C9(H9)
2.d Idealised Me refined as rotating group:
 C54(H54A,H54B,H54C), C41(H41A,H41B,H41C), C28(H28A,H28B,H28C), C13(H13A,H13B,
 H13C)
;
_shelx_res_checksum              28441
_shelx_hkl_checksum              92063
_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 1.754
_oxdiff_exptl_absorpt_empirical_full_min 0.574