Synergistic Diselenide/Guanidine Catalyzed Dehydrophosphorylation of 2-Nitrobenzhydrols to Access C-Stereogenic Phosphinates
Yang, Shang-Dong; Gong, Jin-Yu; Zhou, Panpan; Qiao, Yu-Hao; Qi, Zhichao; Zuo, Qian-Min; Fang, Qing-Xia; Chemical Science  (2026) –; doi:10.1039/D5SC07228J

data_1576901
_publ_section_title
;
 Synergistic diselenide/guanidine catalyzed dehydrophosphorylation of
 2-nitrobenzhydrols to access C-stereogenic phosphinates.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              9526
_journal_page_last               9534
_journal_paper_doi               10.1039/d5sc07228j
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H20 N O4 P'
_chemical_formula_sum            'C25 H20 N O4 P'
_chemical_formula_weight         429.39
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-22 deposited with the CCDC.	2026-03-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.33330(10)
_cell_length_b                   10.33330(10)
_cell_length_c                   39.8477(5)
_cell_measurement_reflns_used    15765
_cell_measurement_temperature    295.22(10)
_cell_measurement_theta_max      75.8280
_cell_measurement_theta_min      4.4040
_cell_volume                     4254.82(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      295.22(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.986
_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    -33.00  -8.00   0.50    0.05    --   44.63 -19.00 120.00   50
  2  \w    -22.00  37.00   0.50    0.05    --   44.63 -37.00 -30.00  118
  3  \w     35.00  66.00   0.50    0.05    --  108.93 -67.00 -26.00   62
  4  \w     42.00 102.00   0.50    0.05    --  108.93 -77.00 -90.00  120
  5  \w    -20.00  14.00   0.50    0.05    --   44.63 -19.00-180.00   68
  6  \w     35.00  60.00   0.50    0.05    --  108.93 -61.00   0.00   50
  7  \w     40.00  65.00   0.50    0.05    --  108.93 -61.00 120.00   50
  8  \w     91.00 161.00   0.50    0.05    --  108.93  30.00  60.00  140
  9  \w     89.00 170.00   0.50    0.05    --  108.93  67.00 107.00  162
 10  \w    130.00 161.00   0.50    0.05    --  108.93  30.00-120.00   62
 11  \w   -116.00 -26.00   0.50    0.05    --  -44.63 -57.00 175.00  180
 12  \w    -53.00 -25.00   0.50    0.05    -- -100.00  45.00  60.00   56
 13  \w    -51.00 -26.00   0.50    0.05    -- -100.00  57.00 -42.00   50
 14  \w    -84.00 -32.00   0.50    0.05    -- -100.00  67.00 107.00  104
 15  \w     38.00 104.00   0.50    0.05    --  108.93 -94.00 -90.00  132
 16  \w    -53.00 -28.00   0.50    0.05    -- -100.00  45.00-180.00   50
 17  \w    -53.00 -25.00   0.50    0.05    -- -100.00  45.00-120.00   56
 18  \w   -103.00 -53.00   0.50    0.05    -- -100.00 108.00-169.00  100
 19  \w    -69.00 -37.00   0.50    0.05    -- -100.00 125.00-150.00   64
 20  \w   -112.00 -72.00   0.50    0.05    -- -100.00 125.00-150.00   80
 21  \w    -79.00 -48.00   0.50    0.05    --  -44.63 179.00   0.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0405857000
_diffrn_orient_matrix_UB_12      -0.0871576000
_diffrn_orient_matrix_UB_13      0.0295523000
_diffrn_orient_matrix_UB_21      0.0933614000
_diffrn_orient_matrix_UB_22      -0.0738515000
_diffrn_orient_matrix_UB_23      -0.0232671000
_diffrn_orient_matrix_UB_31      0.1089514000
_diffrn_orient_matrix_UB_32      0.0957201000
_diffrn_orient_matrix_UB_33      0.0089716000
_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  0.0404
_diffrn_reflns_av_unetI/netI     0.0216
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            24608
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.204
_diffrn_reflns_theta_min         4.420
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.416
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38038
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             1792
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.154
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.028
_refine_ls_abs_structure_details
;
 Flack x determined using 1463 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     280
_refine_ls_number_reflns         4340
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0370
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0583P)^2^+0.2134P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0923
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.649
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3968
_reflns_number_total             4340
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07228j2.cif
_cod_data_source_block           gongjinyu2-yshd_1218_auto
_cod_depositor_comments          'Adding full bibliography for 1576901.cif.'
_cod_original_cell_volume        4254.82(10)
_cod_database_code               1576901
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9), C11(H11), C13(H13),
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C21(H21), C22(H22), C23(H23),
  C24(H24), C25(H25)
;
_shelx_res_checksum              43164
_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 1.950
_oxdiff_exptl_absorpt_empirical_full_min 0.731