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_1576798
_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         'C36 H42 F10 N4 P2, 2(C F3 O3 S)'
_chemical_formula_sum            'C38 H42 F16 N4 O6 P2 S2'
_chemical_formula_weight         1080.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-01-12
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2025-11-07 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.4910(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.94280(10)
_cell_length_b                   14.67850(10)
_cell_length_c                   14.0224(2)
_cell_measurement_reflns_used    11104
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3020
_cell_measurement_theta_min      4.0840
_cell_volume                     2233.11(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -109.00 -15.00   0.50    0.50    --  -38.50 -44.00-146.00  188
  2  \w    -47.00 -17.00   0.50    0.50    --  -38.50  44.00   4.00   60
  3  \w     -5.00  20.00   0.50    0.50    --   42.75 -44.00-146.00   50
  4  \w     59.00 113.00   0.50    0.50    --   42.75  44.00   4.00  108
  5  \w     92.00 119.00   0.50    2.00    --  111.00 -44.00-146.00   54
  6  \w     89.00 158.00   0.50    2.00    --  111.00  44.00   4.00  138
  7  \w    -60.00  31.00   0.50    0.50    --  -38.50  38.00-180.00  182
  8  \w    -82.00 -51.00   0.50    0.50    --  -38.50 125.00  30.00   62
  9  \w    -36.00  -6.00   0.50    0.50    --  -38.50 125.00  30.00   60
 10  \w    -15.00  31.00   0.50    0.50    --  -38.50  44.00   4.00   92
 11  \w     58.00  96.00   0.50    0.50    --   42.75-125.00-180.00   76
 12  \w     12.00  76.00   0.50    0.50    --   42.75 -99.00  30.00  128
 13  \w    124.00 151.00   0.50    2.00    --  111.00  77.00 -60.00   54
 14  \w     92.00 154.00   0.50    2.00    --  111.00  45.00-120.00  124
 15  \w    105.00 132.00   0.50    2.00    --  111.00  77.00 -90.00   54
 16  \w     30.00  73.00   0.50    2.00    --  111.00 -94.00-180.00   86
 17  \w     58.00  91.00   0.50    2.00    --  111.00-125.00 150.00   66
 18  \w     51.00 112.00   0.50    2.00    --  111.00-125.00-180.00  122
 19  \w     58.00 107.00   0.50    2.00    --  111.00 -94.00   0.00   98
 20  \w     42.00 112.00   0.50    2.00    --  111.00-125.00 -60.00  140
 21  \w     81.00 106.00   0.50    2.00    --  111.00 -94.00 150.00   50
 22  \w     63.00  90.00   0.50    2.00    --  111.00 -61.00 -60.00   54
 23  \w     99.00 126.00   0.50    2.00    --  111.00 125.00   0.00   54
 24  \w    105.00 177.00   0.50    2.00    --  111.00  77.00  60.00  144
 25  \w    137.00 162.00   0.50    2.00    --  111.00 125.00   0.00   50
 26  \w     73.00 103.00   0.50    2.00    --  111.00 -94.00 -60.00   60
 27  \w     32.00 102.00   0.50    2.00    --  111.00 -94.00 -30.00  140
 28  \w     32.00  67.00   0.50    2.00    --  111.00 -94.00  60.00   70
 29  \w     75.00 105.00   0.50    2.00    --  111.00 -94.00-180.00   60
 30  \w     87.00 176.00   0.50    2.00    --  111.00  45.00 120.00  178
 31  \w    103.00 143.00   0.50    2.00    --  111.00 125.00 -60.00   80
 32  \w    125.00 176.00   0.50    2.00    --  111.00  77.00-180.00  102
 33  \w     44.00  69.00   0.50    2.00    --  111.00 -94.00 -60.00   50
 34  \w     42.00  84.00   0.50    2.00    --  111.00-125.00-120.00   84
 35  \w     77.00 107.00   0.50    2.00    --  111.00 -94.00 -90.00   60
 36  \w     39.00 107.00   0.50    2.00    --  111.00 -94.00  30.00  136
 37  \w     68.00 107.00   0.50    2.00    --  111.00 -99.00-140.39   78
 38  \w     68.00 107.00   0.50    2.00    --  111.00 -94.00  60.00   78
 39  \w     30.00  70.00   0.50    2.00    --  111.00 -94.00  90.00   80
;
_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      0.1286379000
_diffrn_orient_matrix_UB_12      0.0183173000
_diffrn_orient_matrix_UB_13      0.0555970000
_diffrn_orient_matrix_UB_21      -0.0353175000
_diffrn_orient_matrix_UB_22      -0.0548054000
_diffrn_orient_matrix_UB_23      0.0859359000
_diffrn_orient_matrix_UB_31      0.0487108000
_diffrn_orient_matrix_UB_32      -0.0877251000
_diffrn_orient_matrix_UB_33      -0.0421950000
_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  0.0253
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            24861
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.627
_diffrn_reflns_theta_min         4.380
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.833
_exptl_absorpt_correction_T_max  0.767
_exptl_absorpt_correction_T_min  0.631
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.607
_exptl_crystal_description       block
_exptl_crystal_F_000             1104
_exptl_crystal_size_max          0.235
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.133
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     343
_refine_ls_number_reflns         4675
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0418
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0577P)^2^+1.1086P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1037
_refine_ls_wR_factor_ref         0.1071
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4283
_reflns_number_total             4675
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1722
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576798
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C38H40F16N4O6P2S2
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
C9A \\sim C10A \\sim C11A \\sim C9B \\sim C10B \\sim C11B: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C11B)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=1-FVAR(1)
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11A)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C4(H4), C12(H12), C9A(H9A), C9B(H9B)
4.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10A(H10A,
 H10B,H10C), C11A(H11A,H11B,H11C), C10B(H10D,H10E,H10F), C11B(H11D,H11E,H11F)
;
_shelx_res_checksum              12719
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.820