Deoxygenative Phosphonation of Ketones by Titanium
Wang, Yuquan; Yin, Kai; Pang, Xiaobo; Shu, Xing-Zhong; Chemical Science  (2026) –; doi:10.1039/D5SC09520D

data_1576503
_publ_section_title
;
 Deoxygenative phosphonation of ketones by titanium.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              7236
_journal_page_last               7243
_journal_paper_doi               10.1039/d5sc09520d
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C37 H55 O2 P Si'
_chemical_formula_sum            'C37 H55 O2 P Si'
_chemical_formula_weight         590.87
_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     dual
_audit_creation_date             2025-06-26
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-06-27 deposited with the CCDC.	2026-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.16070(10)
_cell_length_b                   16.4581(2)
_cell_length_c                   33.3457(4)
_cell_measurement_reflns_used    14501
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      75.9980
_cell_measurement_theta_min      2.6380
_cell_volume                     3381.03(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-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.957
_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     41.00  66.00   0.50    0.24    --  108.90 -61.00-150.00   50
  2  \w     38.00  63.00   0.50    0.24    --  108.90 -61.00 -30.00   50
  3  \w     73.00  99.00   0.50    0.24    --  108.90 -77.00  30.00   52
  4  \w     39.00  70.00   0.50    0.24    --  108.90 -77.00  30.00   62
  5  \w     35.00  68.00   0.50    0.24    --  108.90 -61.00  60.00   66
  6  \w     -1.00  96.00   0.50    0.06    --   44.41   2.00 -18.00  194
  7  \w     80.00 105.00   0.50    0.24    --  108.90 -94.00-120.00   50
  8  \w     78.00 103.00   0.50    0.24    --  108.90 -94.00-150.00   50
  9  \w     35.00  68.00   0.50    0.24    --  108.90 -94.00-150.00   66
 10  \w     37.00 104.00   0.50    0.24    --  108.90 -94.00 120.00  134
 11  \w   -117.00 -84.00   0.50    0.24    -- -100.00 132.00 168.00   66
 12  \w   -112.00 -67.00   0.50    0.24    -- -100.00 125.00 120.00   90
 13  \w    -54.00 -29.00   0.50    0.24    -- -100.00 125.00 120.00   50
 14  \w    -30.00   6.00   0.50    0.06    --  -44.41  19.00 120.00   72
 15  \w    -67.00 -26.00   0.50    0.24    -- -100.00  61.00  30.00   82
 16  \w    -54.00 -27.00   0.50    0.24    -- -100.00  45.00   0.00   54
 17  \w   -172.00 -54.00   0.50    0.24    -- -100.00   2.00 -18.00  236
 18  \w   -145.00 -88.00   0.50    0.24    -- -100.00-131.00   8.00  114
 19  \w   -120.00 -75.00   0.50    0.06    --  -44.41-179.00 -60.00   90
;
_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      -0.0023204000
_diffrn_orient_matrix_UB_12      -0.0646406000
_diffrn_orient_matrix_UB_13      0.0334172000
_diffrn_orient_matrix_UB_21      -0.0072662000
_diffrn_orient_matrix_UB_22      0.0676920000
_diffrn_orient_matrix_UB_23      0.0318746000
_diffrn_orient_matrix_UB_31      -0.2499487000
_diffrn_orient_matrix_UB_32      -0.0012898000
_diffrn_orient_matrix_UB_33      -0.0012410000
_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  0.0336
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       2
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            17022
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.122
_diffrn_reflns_theta_min         2.650
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.280
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90656
_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    1.161
_exptl_crystal_description       needle
_exptl_crystal_F_000             1288
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.185
_refine_diff_density_min         -0.204
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2572 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         6611
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0313
_refine_ls_R_factor_gt           0.0299
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0344P)^2^+0.5295P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0753
_refine_ls_wR_factor_ref         0.0763
_reflns_Friedel_coverage         0.705
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.903
_reflns_number_gt                6364
_reflns_number_total             6611
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09520d2.cif
_cod_data_source_block           wangyuq_0626_auto
_cod_depositor_comments          'Adding full bibliography for 1576503.cif.'
_cod_database_code               1576503
_shelx_shelxl_version_number     2018/3
_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:
 C6(H6), C15(H15), C38(H38), C40(H40), C63(H63), C86(H86)
2.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C13(H13A,H13B), C21(H21A,H21B), C33(H33A,H33B), C36(H36A,H36B),
 C70(H70A,H70B), C72(H72A,H72B), C80(H80A,H80B), C94(H94A,H94B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C27(H27), C35(H35), C44(H44), C55(H55), C64(H64), C65(H65), C68(H68),
 C69(H69), C75(H75)
2.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C18(H18A,H18B,H18C), C23(H23A,H23B,
 H23C), C56(H56A,H56B,H56C), C77(H77A,H77B,H77C), C91(H91A,H91B,H91C)
;
_shelx_res_checksum              57147
_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 1.166
_oxdiff_exptl_absorpt_empirical_full_min 0.626