Access to P-Chiral sec- and tert-Phosphine Oxides Enabled by Le-Phos-Catalyzed Asymmetric Kinetic Resolution
Qiu, Haile; Dai, Qiang; He, Jiafeng; Li, Wenbo; Zhang, Junliang; Chemical Science  (2020) –; doi:10.1039/D0SC04041J

data_1558957
_publ_section_title
;
 Access to P-Chiral sec- and tert-Phosphine Oxides Enabled by
 Le-Phos-Catalyzed Asymmetric Kinetic Resolution
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04041J
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C22 H31 O P), 0.5(H2 O)'
_chemical_formula_sum            'C44 H63 O2.5 P2'
_chemical_formula_weight         693.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-02-23 deposited with the CCDC.	2020-09-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.8380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.20990(10)
_cell_length_b                   17.2004(2)
_cell_length_c                   21.3573(2)
_cell_measurement_reflns_used    37495
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.2510
_cell_measurement_theta_min      4.7420
_cell_volume                     4069.11(7)
_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     42.00  75.00   1.00    1.00    --    0.00  19.00   0.00   33
  2  \w     25.00  70.00   1.00    1.00    --    0.00  57.00-180.00   45
  3  \w    -12.00  75.00   1.00    1.00    --    0.00  38.00   0.00   87
  4  \w    -23.00  24.00   1.00    1.00    --    0.00  57.00 -90.00   47
  5  \w    -23.00  30.00   1.00    1.00    --    0.00  19.00 120.00   53
  6  \w    -16.00  35.00   1.00    1.00    --    0.00  38.00 150.00   51
  7  \w     42.00  82.00   1.00    1.00    --    0.00  19.00 120.00   40
  8  \w    -23.00   9.00   1.00    1.00    --    0.00  57.00-150.00   32
  9  \w    -22.00  10.00   1.00    1.00    --    0.00  57.00-180.00   32
 10  \w     39.00  88.00   1.00    1.00    --    0.00  57.00 -90.00   49
 11  \w    -22.00  12.00   1.00    1.00    --    0.00  19.00   0.00   34
 12  \w     53.00  85.00   1.00    1.00    --    0.00  38.00 150.00   32
 13  \w     26.00  88.00   1.00    1.00    --    0.00  57.00-150.00   62
 14  \w    -30.00  69.00   1.00    1.00    --    0.00  77.00  30.00   99
 15  \w     81.00 128.00   1.00    1.00    --   95.80 -82.00 120.00   47
 16  \w      7.00 120.00   1.00    1.00    --   95.80 -61.00 -60.00  113
 17  \w     74.00 102.00   1.00    1.00    --   95.80  50.00 -37.62   28
 18  \w     65.00 108.00   1.00    1.00    --   95.80  77.00-149.40   43
 19  \w     68.00 144.00   1.00    1.00    --   95.80  68.00 152.98   76
 20  \w    117.00 171.00   1.00    1.00    --   95.80  77.00  54.03   54
 21  \w     75.00 101.00   1.00    1.00    --   95.80  47.00 127.10   26
 22  \w     63.00  89.00   1.00    1.00    --   95.80  82.00  90.00   26
 23  \w    130.00 156.00   1.00    1.00    --   95.80  82.00  90.00   26
 24  \w     72.00 153.00   1.00    1.00    --   95.80  61.00-180.00   81
 25  \w     63.00  90.00   1.00    1.00    --   95.80  82.00 -90.00   27
 26  \w     63.00  92.00   1.00    1.00    --   95.80  82.00  60.00   29
 27  \w    108.00 185.00   1.00    1.00    --   95.80  82.00  60.00   77
 28  \w     63.00  89.00   1.00    1.00    --   95.80  82.00 120.00   26
 29  \w      6.00 128.00   1.00    1.00    --   95.80 -82.00  60.00  122
 30  \w     69.00 168.00   1.00    1.00    --   95.80  65.00 -83.21   99
 31  \w     65.00  91.00   1.00    1.00    --   95.80  77.00-120.00   26
 32  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 120.00   25
 33  \w     66.00  91.00   1.00    1.00    --   95.80  76.00-159.91   25
 34  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  54.03   25
 35  \w     65.00  90.00   1.00    1.00    --   95.80  77.00  30.00   25
 36  \w     75.00 182.00   1.00    1.00    --   95.80  45.00 150.00  107
 37  \w     65.00 185.00   1.00    1.00    --   95.80  77.00   0.00  120
 38  \w    124.00 150.00   1.00    1.00    --   95.80  77.00 -30.00   26
 39  \w     71.00  96.00   1.00    1.00    --   95.80  61.00 -30.00   25
 40  \w     71.00  97.00   1.00    1.00    --   95.80  61.00  60.00   26
 41  \w     14.00 120.00   1.00    1.00    --   95.80 -61.00  60.00  106
 42  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 -60.00   25
 43  \w     65.00  90.00   1.00    1.00    --   95.80  77.00 150.00   25
 44  \w     65.00  91.00   1.00    1.00    --   95.80  77.00  90.00   26
 45  \w     63.00  88.00   1.00    1.00    --   95.80  82.00   0.00   25
 46  \w     71.00 162.00   1.00    1.00    --   95.80  61.00-150.00   91
 47  \w     71.00 185.00   1.00    1.00    --   95.80  58.00-102.67  114
 48  \w     65.00  91.00   1.00    1.00    --   95.80  77.00 -90.00   26
 49  \w     76.00 148.00   1.00    1.00    --   95.80  45.00   0.00   72
 50  \w     75.00 107.00   1.00    1.00    --   95.80  45.00  60.00   32
 51  \w    112.00 150.00   1.00    1.00    --   95.80  45.00  60.00   38
 52  \w     75.00 105.00   1.00    1.00    --   95.80  45.00  90.00   30
 53  \w     76.00 102.00   1.00    1.00    --   95.80  45.00 120.00   26
 54  \w     69.00  94.00   1.00    1.00    --   95.80  66.00-176.69   25
 55  \w    145.00 170.00   1.00    1.00    --   95.80  82.00 -30.00   25
 56  \w     63.00  88.00   1.00    1.00    --   95.80  82.00 -30.00   25
 57  \w     65.00  95.00   1.00    1.00    --   95.80  77.00 -30.00   30
 58  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-120.00   26
 59  \w     63.00  89.00   1.00    1.00    --   95.80  82.00-150.00   26
 60  \w     66.00  91.00   1.00    1.00    --   95.80  77.00-180.00   25
 61  \w     60.00 122.00   1.00    1.00    --   95.80 -82.00 -60.00   62
 62  \w    120.00 185.00   1.00    1.00    --   95.80  50.00 -37.62   65
 63  \w    117.00 143.00   1.00    1.00    --   95.80  47.00 127.10   26
 64  \w    136.00 182.00   1.00    1.00    --   95.80  79.00 -12.10   46
 65  \w     96.00 122.00   1.00    1.00    --   95.80 -82.00-180.00   26
 66  \w     47.00 102.00   1.00    1.00    --   95.80 -82.00-120.00   55
 67  \w     64.00  90.00   1.00    1.00    --   95.80  79.00 -12.10   26
;
_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      -0.1290706000
_diffrn_orient_matrix_UB_12      -0.0093952000
_diffrn_orient_matrix_UB_13      0.0153146000
_diffrn_orient_matrix_UB_21      0.0487450000
_diffrn_orient_matrix_UB_22      0.0063723000
_diffrn_orient_matrix_UB_23      0.0712636000
_diffrn_orient_matrix_UB_31      -0.0171526000
_diffrn_orient_matrix_UB_32      0.0889037000
_diffrn_orient_matrix_UB_33      -0.0034914000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            46113
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         4.190
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.230
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46554
_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    1.133
_exptl_crystal_description       block
_exptl_crystal_F_000             1508
_exptl_crystal_size_max          0.46
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.28
_refine_diff_density_max         0.246
_refine_diff_density_min         -0.169
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 3109 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(5)
_refine_ls_extinction_coef       0.00030(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     466
_refine_ls_number_reflns         6942
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0269
_refine_ls_R_factor_gt           0.0267
_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^)+(0.0432P)^2^+1.6880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0701
_refine_ls_wR_factor_ref         0.0702
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.902
_reflns_Friedel_fraction_max     0.902
_reflns_number_gt                6895
_reflns_number_total             6942
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04041j2.cif
_cod_data_source_block           exp_923
_cod_original_formula_sum        'C44 H63 O2.50 P2'
_cod_database_code               1558957
_shelx_shelxl_version_number     2016/6
_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, All O(H,H) groups
2. Others
 Fixed Sof: H3A(0.5) H3B(0.5)
3.a Free rotating group:
 O3(H3A,H3B)
3.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C2(H2), C4(H4), C34(H34), C32(H32), C36(H36), C27(H27), C18(H18),
 C26(H26), C17(H17), C16(H16), C25(H25)
3.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C21(H21A,H21B,H21C), C12(H12A,H12B,
 H12C), C13(H13A,H13B,H13C), C44(H44A,H44B,H44C), C9(H9A,H9B,H9C), C14(H14A,
 H14B,H14C), C42(H42A,H42B,H42C), C22(H22A,H22B,H22C), C38(H38A,H38B,H38C),
 C43(H43A,H43B,H43C), C39(H39A,H39B,H39C), C30(H30A,H30B,H30C), C29(H29A,H29B,
 H29C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              39300
_shelx_fab_checksum              17719
_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 1.663
_oxdiff_exptl_absorpt_empirical_full_min 0.602