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_4133760
_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 rmad
_chemical_formula_moiety         'C72 H88 Cl2 N2 O2 P2 Pd S2'
_chemical_formula_sum            'C72 H88 Cl2 N2 O2 P2 Pd S2'
_chemical_formula_weight         1316.80
_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             2019-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 103.9040(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.51660(10)
_cell_length_b                   10.26470(10)
_cell_length_c                   25.2392(2)
_cell_measurement_reflns_used    58976
_cell_measurement_temperature    100.01(11)
_cell_measurement_theta_max      74.3890
_cell_measurement_theta_min      4.0220
_cell_volume                     4153.63(6)
_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(11)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_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    -19.00  62.00   1.00    1.00    --    0.00  38.00 150.00   81
  2  \w    -21.00  14.00   1.00    1.00    --    0.00  57.00  60.00   35
  3  \w    -18.00  89.00   1.00    1.00    --    0.00  38.00 -60.00  107
  4  \w    -23.00  21.00   1.00    1.00    --    0.00  19.00 150.00   44
  5  \w    -45.00  -1.00   1.00    1.00    --    0.00 -57.00 120.00   44
  6  \w    -19.00  75.00   1.00    1.00    --    0.00  38.00-120.00   94
  7  \w     27.00  87.00   1.00    1.00    --    0.00  38.00   0.00   60
  8  \w     37.00  86.00   1.00    1.00    --    0.00  77.00 150.00   49
  9  \w     37.00  85.00   1.00    1.00    --    0.00  38.00  30.00   48
 10  \w    -18.00   8.00   1.00    1.00    --    0.00  38.00  30.00   26
 11  \w     18.00  77.00   1.00    1.00    --    0.00  57.00  60.00   59
 12  \w    -19.00  20.00   1.00    1.00    --    0.00  38.00   0.00   39
 13  \w     -5.00  29.00   1.00    1.00    --    0.00  77.00 150.00   34
 14  \w    -87.00 -52.00   1.00    1.00    --    0.00 -57.00 120.00   35
 15  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -65.13   26
 16  \w     64.00  90.00   1.00    1.00    --   95.80  79.00 129.83   26
 17  \w     63.00  89.00   1.00    1.00    --   95.80  81.00  75.91   26
 18  \w    126.00 168.00   1.00    1.00    --   95.80  50.00  -5.06   42
 19  \w     74.00 116.00   1.00    1.00    --   95.80  50.00  -5.06   42
 20  \w     66.00  96.00   1.00    1.00    --   95.80  74.00-126.39   30
 21  \w     70.00 134.00   1.00    1.00    --   95.80  63.00  69.28   64
 22  \w     64.00  90.00   1.00    1.00    --   95.80  80.00  24.73   26
 23  \w    148.00 182.00   1.00    1.00    --   95.80  80.00  24.73   34
 24  \w      6.00  49.00   1.00    1.00    --   95.80 -82.00 -60.00   43
 25  \w     53.00 106.00   1.00    1.00    --   95.80 -82.00 -60.00   53
 26  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -30.00   26
 27  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-150.00   25
 28  \w     90.00 128.00   1.00    1.00    --   95.80 -82.00  60.00   38
 29  \w     49.00 128.00   1.00    1.00    --   95.80 -82.00-150.00   79
 30  \w     64.00 154.00   1.00    1.00    --   95.80  80.00 106.41   90
 31  \w     68.00  94.00   1.00    1.00    --   95.80  68.00-144.92   26
 32  \w    127.00 177.00   1.00    1.00    --   95.80  76.00-100.25   50
 33  \w     65.00  91.00   1.00    1.00    --   95.80  76.00-100.25   26
 34  \w    143.00 169.00   1.00    1.00    --   95.80  54.00  37.16   26
 35  \w     72.00 129.00   1.00    1.00    --   95.80  57.00 160.81   57
 36  \w     64.00  90.00   1.00    1.00    --   95.80  82.00  30.00   26
 37  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 38  \w     67.00  93.00   1.00    1.00    --   95.80  72.00 149.93   26
 39  \w     65.00 143.00   1.00    1.00    --   95.80  77.00-120.00   78
 40  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -60.00   25
 41  \w    102.00 184.00   1.00    1.00    --   95.80  82.00 -60.00   82
 42  \w     12.00  49.00   1.00    1.00    --   95.80 -82.00 150.00   37
 43  \w     58.00 128.00   1.00    1.00    --   95.80 -82.00 150.00   70
 44  \w     71.00 147.00   1.00    1.00    --   95.80  61.00 -60.00   76
 45  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 46  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 150.00   26
 47  \w     63.00  88.00   1.00    1.00    --   95.80  82.00-180.00   25
 48  \w     63.00  88.00   1.00    1.00    --   95.80  82.00  60.00   25
 49  \w     65.00 147.00   1.00    1.00    --   95.80  77.00 120.00   82
 50  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 51  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  60.00   25
 52  \w    111.00 182.00   1.00    1.00    --   95.80  81.00  12.51   71
 53  \w     73.00 120.00   1.00    1.00    --   95.80  54.00  37.16   47
 54  \w     75.00 103.00   1.00    1.00    --   95.80  45.00  30.00   28
 55  \w      9.00 128.00   1.00    1.00    --   95.80 -82.00   0.00  119
 56  \w      6.00 118.00   1.00    1.00    --   95.80 -61.00   0.00  112
 57  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-120.00   26
 58  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 -90.00   26
 59  \w     71.00  98.00   1.00    1.00    --   95.80  61.00  60.00   27
 60  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 61  \w    129.00 178.00   1.00    1.00    --   95.80  77.00   0.00   49
 62  \w     63.00  89.00   1.00    1.00    --   95.80  81.00  12.51   26
 63  \w     71.00  97.00   1.00    1.00    --   95.80  61.00 -30.00   26
 64  \w     65.00  90.00   1.00    1.00    --   95.80  77.00-180.00   25
 65  \w     65.00  90.00   1.00    1.00    --   95.80  77.00   0.00   25
 66  \w     75.00 180.00   1.00    1.00    --   95.80  45.00-120.00  105
 67  \w    111.00 185.00   1.00    1.00    --   95.80  61.00 -30.00   74
 68  \w     65.00 114.00   1.00    1.00    --   95.80  77.00  90.00   49
 69  \w     75.00 178.00   1.00    1.00    --   95.80  45.00-150.00  103
 70  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -90.00   25
 71  \w    151.00 176.00   1.00    1.00    --   95.80  77.00 -65.13   25
 72  \w    159.00 184.00   1.00    1.00    --   95.80  81.00  75.91   25
 73  \w     71.00 172.00   1.00    1.00    --   95.80  61.00  90.00  101
 74  \w    147.00 172.00   1.00    1.00    --   95.80  63.00  69.28   25
 75  \w     73.00  99.00   1.00    1.00    --   95.80  53.00-154.94   26
 76  \w     72.00 163.00   1.00    1.00    --   95.80  57.00-177.20   91
;
_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      -0.0957228000
_diffrn_orient_matrix_UB_12      0.0066632000
_diffrn_orient_matrix_UB_13      -0.0194646000
_diffrn_orient_matrix_UB_21      -0.0044837000
_diffrn_orient_matrix_UB_22      0.0644406000
_diffrn_orient_matrix_UB_23      0.0542972000
_diffrn_orient_matrix_UB_31      0.0069237000
_diffrn_orient_matrix_UB_32      0.1355410000
_diffrn_orient_matrix_UB_33      -0.0248861000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1075
_diffrn_reflns_av_unetI/netI     0.0531
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            110584
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.680
_diffrn_reflns_theta_min         3.608
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.508
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.12290
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.053
_exptl_crystal_description       block
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.862
_refine_diff_density_min         -1.018
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 6813 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     770
_refine_ls_number_reflns         16519
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0478
_refine_ls_R_factor_gt           0.0464
_refine_ls_shift/su_max          0.030
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0584P)^2^+2.9384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1155
_refine_ls_wR_factor_ref         0.1166
_reflns_Friedel_coverage         0.849
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.946
_reflns_number_gt                15856
_reflns_number_total             16519
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11938_si_003.cif
_cod_data_source_block           exp_944
_cod_depositor_comments
'Adding full bibliography for 4133759--4133760.cif.'
_cod_database_code               4133760
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.512
_shelx_estimated_absorpt_t_min   0.295
_reflns_odcompleteness_completeness 99.95
_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
2.a Ternary CH refined with riding coordinates:
 C14(H14), C31(H31), C34(H34), C50(H50), C67(H67), C70(H70)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13a,H13b), C49(H49a,H49b)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2a), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C21(H21), C22(H22), C23(H23), C24(H24), C27(H27), C28(H28), C29(H29),
  C38(H38), C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45),
 C46(H46), C47(H47), C48(H48), C57(H57), C58(H58), C59(H59), C60(H60), C63(H63),
  C64(H64), C65(H65)
2.d Idealised Me refined as rotating group:
 C16(H16a,H16b,H16c), C17(H17a,H17b,H17c), C18(H18a,H18b,H18c), C32(H32a,H32b,
 H32c), C33(H33a,H33b,H33c), C35(H35a,H35b,H35c), C36(H36a,H36b,H36c), C52(H52a,
 H52b,H52c), C53(H53a,H53b,H53c), C54(H54a,H54b,H54c), C68(H68a,H68b,H68c),
 C69(H69a,H69b,H69c), C71(H71a,H71b,H71c), C72(H72a,H72b,H72c)
;
_shelx_res_checksum              7681
_shelx_hkl_checksum              93694
_shelx_fab_checksum              77241
_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 5.631
_oxdiff_exptl_absorpt_empirical_full_min 0.342