Chemoselectivity in the cationic Phospha-Wittig reaction: accessing phosphorus heterocycles, phosphaalkenes, and their annulated [4 + 2] dimers.
Royla, Philipp; Schwedtmann, Kai; Gomila, Rosa M.; Frontera, Antonio; Weigand, Jan J.; Chemical science 17 (2025) 4678–4687; doi:10.1039/d5sc08693k

data_1576802
_publ_section_title
;
 Chemoselectivity in the cationic Phospha-Wittig reaction: accessing
 phosphorus heterocycles, phosphaalkenes, and their annulated [4 + 2]
 dimers.
;
_journal_issue                   9
_journal_name_full               'Chemical science'
_journal_page_first              4678
_journal_page_last               4687
_journal_paper_doi               10.1039/d5sc08693k
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C24 H33 N3 O2 P, C F3 O3 S'
_chemical_formula_sum            'C25 H33 F3 N3 O5 P S'
_chemical_formula_weight         575.57
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-12-10
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2025-12-20 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.322(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9283(4)
_cell_length_b                   14.6147(3)
_cell_length_c                   16.8837(6)
_cell_measurement_reflns_used    5156
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3660
_cell_measurement_theta_min      3.9940
_cell_volume                     2684.94(15)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.992
_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     -7.00  29.00   0.50    6.00    --  -38.50  83.00  36.00   72
  2  \w     -7.00  76.00   0.50    6.00    --   42.50 -83.00 -84.00  166
  3  \w    103.00 131.00   0.50   30.00    --  111.00 -83.00 -84.00   56
  4  \w    102.00 169.00   0.50   30.00    --  111.00  83.00  36.00  134
  5  \w    -15.00  70.00   0.50    6.00    --   42.50 -77.00  90.00  170
  6  \w     16.00  44.00   0.50    6.00    --   42.50  57.00 150.00   56
  7  \w     46.00  78.00   0.50    6.00    --   42.50  38.00-150.00   64
  8  \w     60.00 112.00   0.50    6.00    --   42.50  57.00 150.00  104
  9  \w     19.00 113.00   0.50    6.00    --   42.50  57.00-120.00  188
 10  \w    -28.00  66.00   0.50    6.00    --   42.50 -57.00   0.00  188
 11  \w     40.00 134.00   0.50   30.00    --  111.00 -45.00 -90.00  188
 12  \w     44.00 108.00   0.50   30.00    --  111.00-125.00 120.00  128
 13  \w     42.00  82.00   0.50   30.00    --  111.00-125.00 -30.00   80
 14  \w    115.00 157.00   0.50   30.00    --  111.00  77.00-180.00   84
 15  \w    108.00 136.00   0.50   30.00    --  111.00  77.00-120.00   56
 16  \w     38.00 152.00   0.50   30.00    --  111.00 -15.00  30.00  228
 17  \w     30.00 107.00   0.50   30.00    --  111.00 -94.00-150.00  154
 18  \w     38.00  75.00   0.50   30.00    --  111.00 -94.00 150.00   74
 19  \w    105.00 153.00   0.50   30.00    --  111.00 125.00   0.00   96
 20  \w     88.00 169.00   0.50   30.00    --  111.00  30.00  90.00  162
 21  \w     55.00 100.00   0.50   30.00    --  111.00 -94.00-120.00   90
 22  \w     46.00 107.00   0.50   30.00    --  111.00-100.00  14.76  122
 23  \w     88.00 116.00   0.50   30.00    --  111.00  45.00-120.00   56
 24  \w     43.00 107.00   0.50   30.00    --  111.00 -94.00 -90.00  128
 25  \w     41.00  89.00   0.50   30.00    --  111.00-125.00  90.00   96
 26  \w     71.00 112.00   0.50   30.00    --  111.00-125.00   0.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0343266000
_diffrn_orient_matrix_UB_12      -0.0547874000
_diffrn_orient_matrix_UB_13      -0.0727340000
_diffrn_orient_matrix_UB_21      0.1359976000
_diffrn_orient_matrix_UB_22      0.0009931000
_diffrn_orient_matrix_UB_23      0.0335346000
_diffrn_orient_matrix_UB_31      -0.0193479000
_diffrn_orient_matrix_UB_32      -0.0899881000
_diffrn_orient_matrix_UB_33      0.0446093000
_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  0.0592
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            20867
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         4.008
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.183
_exptl_absorpt_correction_T_max  0.935
_exptl_absorpt_correction_T_min  0.801
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
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    1.424
_exptl_crystal_description       needle
_exptl_crystal_F_000             1208
_exptl_crystal_size_max          0.146
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.252
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     357
_refine_ls_number_reflns         4874
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0861
_refine_ls_R_factor_gt           0.0712
_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^)+(0.1119P)^2^+2.5709P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1887
_refine_ls_wR_factor_ref         0.1999
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3919
_reflns_number_total             4874
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1470
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576802
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C25H33F3N3O5PS
_reflns_odcompleteness_completeness 97.59
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 C4-H4
 0.9 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C9(H9), C22(H22), C19(H19)
3.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B)
3.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C20(H20), C15(H15), C18(H18), C14(H14), C17(H17)
3.d Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C5(H5A,H5B,H5C),
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C)
;
_shelx_res_checksum              34597
_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 1.787
_oxdiff_exptl_absorpt_empirical_full_min 0.710