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_1576803
_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_absolute_configuration ad
_chemical_formula_moiety         'C29 H41 F5 N4 P2, 2(C F3 O3 S)'
_chemical_formula_sum            'C31 H41 F11 N4 O6 P2 S2'
_chemical_formula_weight         900.74
_space_group_crystal_system      tetragonal
_space_group_IT_number           76
_space_group_name_Hall           'P 4w'
_space_group_name_H-M_alt        'P 41'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-12-17
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-20 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.68062(4)
_cell_length_b                   13.68062(4)
_cell_length_c                   22.05367(11)
_cell_measurement_reflns_used    33205
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4310
_cell_measurement_theta_min      3.2250
_cell_volume                     4127.55(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.121a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.118a 64-bit (release 22-07-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.121a (Rigaku OD, 2025)'
_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      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_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   -118.00  48.00   0.50    0.50    --  -38.50   0.00 -90.00  332
  2  \w    -59.00  19.00   0.50    0.50    --  -38.50  38.00 120.00  156
  3  \w     32.00  83.00   0.50    0.50    --   42.75-125.00-150.00  102
  4  \w     30.00  89.00   0.50    0.50    --   42.75-125.00  30.00  118
  5  \w     12.00  46.00   0.50    0.50    --   42.75 -99.00 -90.00   68
  6  \w    113.00 154.00   0.50    2.00    --  111.00  77.00   0.00   82
  7  \w    101.00 151.00   0.50    2.00    --  111.00 -15.00   0.00  100
  8  \w     38.00  79.00   0.50    2.00    --  111.00 -77.00-180.00   82
  9  \w     88.00 177.00   0.50    2.00    --  111.00  45.00-180.00  178
 10  \w     91.00 157.00   0.50    2.00    --  111.00  30.00 -30.00  132
 11  \w     36.00  71.00   0.50    2.00    --  111.00 -94.00 -90.00   70
 12  \w     82.00 107.00   0.50    2.00    --  111.00 -94.00 -90.00   50
 13  \w     45.00 112.00   0.50    2.00    --  111.00 -61.00  30.00  134
 14  \w    110.00 178.00   0.50    2.00    --  111.00  77.00-120.00  136
 15  \w     31.00  65.00   0.50    2.00    --  111.00 -15.00   0.00   68
 16  \w     80.00 111.00   0.50    2.00    --  111.00-125.00-120.00   62
 17  \w     44.00  69.00   0.50    2.00    --  111.00-125.00-120.00   50
 18  \w     43.00 103.00   0.50    2.00    --  111.00 -45.00-120.00  120
 19  \w    138.00 165.00   0.50    2.00    --  111.00  30.00 -90.00   54
 20  \w     37.00  69.00   0.50    2.00    --  111.00 -94.00  60.00   64
 21  \w     72.00 107.00   0.50    2.00    --  111.00 -94.00  60.00   70
 22  \w     32.00  72.00   0.50    2.00    --  111.00 -94.00-120.00   80
 23  \w     78.00 107.00   0.50    2.00    --  111.00 -94.00-120.00   58
 24  \w     74.00 106.00   0.50    2.00    --  111.00 -94.00 150.00   64
 25  \w     66.00 107.00   0.50    2.00    --  111.00 -94.00 -30.00   82
 26  \w     45.00 110.00   0.50    2.00    --  111.00-125.00-180.00  130
 27  \w     30.00 106.00   0.50    2.00    --  111.00 -94.00   0.00  152
 28  \w     88.00 130.00   0.50    2.00    --  111.00  30.00 -90.00   84
 29  \w     36.00  63.00   0.50    2.00    --  111.00 -94.00 120.00   54
 30  \w    134.00 167.00   0.50    2.00    --  111.00  77.00-150.00   66
 31  \w    107.00 140.00   0.50    2.00    --  111.00 -77.00-180.00   66
 32  \w     51.00  79.00   0.50    2.00    --  111.00-125.00-150.00   56
 33  \w     82.00 109.00   0.50    2.00    --  111.00-125.00 -90.00   54
 34  \w     77.00 104.00   0.50    2.00    --  111.00-125.00   0.00   54
 35  \w    108.00 142.00   0.50    2.00    --  111.00  77.00 -30.00   68
 36  \w     32.00 105.00   0.50    2.00    --  111.00 -94.00  30.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0193670000
_diffrn_orient_matrix_UB_12      -0.1099345000
_diffrn_orient_matrix_UB_13      0.0092994000
_diffrn_orient_matrix_UB_21      0.0001508000
_diffrn_orient_matrix_UB_22      0.0152520000
_diffrn_orient_matrix_UB_23      0.0692291000
_diffrn_orient_matrix_UB_31      -0.1108911000
_diffrn_orient_matrix_UB_32      0.0191389000
_diffrn_orient_matrix_UB_33      -0.0016123000
_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  0.0261
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            46471
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.663
_diffrn_reflns_theta_min         3.230
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.763
_exptl_absorpt_correction_T_max  0.840
_exptl_absorpt_correction_T_min  0.810
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.121a (Rigaku Oxford Diffraction, 2025)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.449
_exptl_crystal_description       block
_exptl_crystal_F_000             1856
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.174
_refine_diff_density_max         0.912
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 3877 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.004(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     590
_refine_ls_number_reflns         8443
_refine_ls_number_restraints     223
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0276
_refine_ls_R_factor_gt           0.0273
_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^)+(0.0392P)^2^+1.1874P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0710
_refine_ls_wR_factor_ref         0.0712
_reflns_Friedel_coverage         0.896
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.944
_reflns_number_gt                8360
_reflns_number_total             8443
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw2010
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576803
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C31H41F11N4O6P2S2
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name ROY17122025_2Cu.xpar
_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. Uiso/Uaniso restraints and constraints
S2A \\sim F9A \\sim F10A \\sim F11A \\sim O4A \\sim O5A \\sim O6A \\sim C31A
\\sim S2B \\sim F9B \\sim F10B \\sim F11B \\sim O4B \\sim O5B \\sim O6B \\sim
C31B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
3. Others
 Sof(S2B)=Sof(F9B)=Sof(F10B)=Sof(F11B)=Sof(O4B)=Sof(O5B)=Sof(O6B)=Sof(C31B)=1-
 FVAR(1)
 Sof(S2A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=Sof(C31A)=
 FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C13(H13), C20(H20), C23(H23)
4.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C)
;
_shelx_res_checksum              84958
_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 1.255
_oxdiff_exptl_absorpt_empirical_full_min 0.854