Asymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to access <i>P</i>-chiral 2-azaaryl-ethylphosphine oxides.
Zhang, Jialiang; Guo, Jiajia; Xu, Ruhui; Zheng, Di; Lian, Kai; Zhang, Zhaoxia; Cao, Shanshan; Jiang, Zhiyong; Chemical science 16 (2025) 5957–5966; doi:10.1039/d5sc00358j

data_1574042
_publ_section_title
;
 Asymmetric copper-catalyzed hydrophosphinylation of ethynylazaarenes to
 access <i>P</i>-chiral 2-azaaryl-ethylphosphine oxides.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5957
_journal_page_last               5966
_journal_paper_doi               10.1039/d5sc00358j
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H22 N O P'
_chemical_formula_sum            'C18 H22 N O P'
_chemical_formula_weight         299.33
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_block_doi                 10.5517/ccdc.csd.cc2l9198
_audit_creation_date             2024-10-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-10-18 deposited with the CCDC.	2025-03-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9528(3)
_cell_length_b                   10.6897(3)
_cell_length_c                   16.8353(5)
_cell_measurement_reflns_used    3651
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8300
_cell_measurement_theta_min      4.4480
_cell_volume                     1791.15(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.102a (Rigaku OD, 2023)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.987
_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   -102.00 -30.00   1.00    1.00    --  -33.50 -57.00   0.00   72
  2  \w     14.00  43.00   1.00    1.00    --   36.47 -57.00-120.00   29
  3  \w    -16.00  62.00   1.00    1.00    --   36.47 -77.00-150.00   78
  4  \w      9.00  69.00   1.00    1.00    --   36.47 -99.00  30.00   60
  5  \w    -23.00   3.00   1.00    1.00    --   36.47 -57.00-120.00   26
  6  \w     39.00 102.00   1.00    1.00    --   36.47  37.00  30.00   63
  7  \w    136.00 167.00   1.00    4.00    --  108.00  77.00-150.00   31
  8  \w    102.00 128.00   1.00    4.00    --  108.00  77.00-150.00   26
  9  \w    103.00 168.00   1.00    4.00    --  108.00  77.00 150.00   65
 10  \w     98.00 132.00   1.00    4.00    --  108.00 -77.00-180.00   34
 11  \w    109.00 177.00   1.00    4.00    --  108.00  77.00  90.00   68
 12  \w     46.00  82.00   1.00    4.00    --  108.00 -77.00-180.00   36
 13  \w     76.00 117.00   1.00    4.00    --  108.00 178.00  60.00   41
 14  \w     48.00 107.00   1.00    4.00    --  108.00-111.00  60.00   59
 15  \w     52.00 136.00   1.00    4.00    --  108.00 -77.00  60.00   84
 16  \w     79.00 146.00   1.00    4.00    --  108.00 178.00  90.00   67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0385102000
_diffrn_orient_matrix_UB_12      0.1321913000
_diffrn_orient_matrix_UB_13      0.0285208000
_diffrn_orient_matrix_UB_21      -0.1105960000
_diffrn_orient_matrix_UB_22      -0.0064516000
_diffrn_orient_matrix_UB_23      0.0639857000
_diffrn_orient_matrix_UB_31      0.1010705000
_diffrn_orient_matrix_UB_32      -0.0570555000
_diffrn_orient_matrix_UB_33      0.0589538000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0313
_diffrn_reflns_av_unetI/netI     0.0471
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6722
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.920
_diffrn_reflns_theta_min         4.901
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.338
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.102a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.110
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.346
_refine_diff_density_min         -0.311
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Flack x determined using 1213 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     194
_refine_ls_number_reflns         3378
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0506
_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^)+(0.0907P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1350
_refine_ls_wR_factor_ref         0.1411
_reflns_Friedel_coverage         0.724
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3110
_reflns_number_total             3378
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00358j2.cif
_cod_data_source_block           zjl_auto
_cod_depositor_comments          'Adding full bibliography for 1574042.cif.'
_cod_database_code               1574042
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C12H22O1N1
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.825
_reflns_odcompleteness_completeness 99.89
_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 Ternary CH refined with riding coordinates:
 C8(H8)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C6(H6), C7(H7), C12(H12), C14(H14), C16(H16)
2.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              91399
_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 1.151
_oxdiff_exptl_absorpt_empirical_full_min 0.912