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_1576799
_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         'C38 H50 N6 P2, 2(C F3 O3 S)'
_chemical_formula_sum            'C40 H50 F6 N6 O6 P2 S2'
_chemical_formula_weight         950.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-09
_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                 109.348(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.0983(7)
_cell_length_b                   9.1242(2)
_cell_length_c                   20.5645(4)
_cell_measurement_reflns_used    5660
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.9970
_cell_measurement_theta_min      4.8280
_cell_volume                     4443.35(19)
_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 0.991
_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    -80.00   7.00   0.50    4.00    --  -38.50 105.00 104.00  174
  2  \w     40.00  67.00   0.50    4.00    --   42.50-105.00   4.00   54
  3  \w    126.00 156.00   0.50   16.00    --  111.00 105.00 104.00   60
  4  \w     64.00 108.00   0.50   16.00    --  111.00-105.00   4.00   88
  5  \w   -109.00 -16.00   0.50    4.00    --  -38.50 -38.00 -60.00  186
  6  \w   -103.00 -27.00   0.50    4.00    --  -38.50 -38.00  30.00  152
  7  \w     20.00  93.00   0.50    4.00    --   42.50  57.00-120.00  146
  8  \w      6.00  71.00   0.50    4.00    --   42.50 -99.00 -90.00  130
  9  \w     88.00 169.00   0.50   16.00    --  111.00  30.00  30.00  162
 10  \w     60.00 100.00   0.50   16.00    --  111.00-125.00 -60.00   80
 11  \w     45.00  73.00   0.50   16.00    --  111.00 -77.00 150.00   56
 12  \w    101.00 156.00   0.50   16.00    --  111.00 125.00  60.00  110
 13  \w     95.00 151.00   0.50   16.00    --  111.00  30.00-180.00  112
 14  \w     30.00 107.00   0.50   16.00    --  111.00 -94.00 120.00  154
 15  \w     31.00  96.00   0.50   16.00    --  111.00 -15.00-180.00  130
 16  \w     56.00 106.00   0.50   16.00    --  111.00 -94.00-180.00  100
 17  \w     33.00 107.00   0.50   16.00    --  111.00 -94.00-150.00  148
 18  \w     41.00  91.00   0.50   16.00    --  111.00-125.00   0.00  100
 19  \w     42.00 106.00   0.50   16.00    --  111.00 -45.00-180.00  128
 20  \w     58.00  85.00   0.50   16.00    --  111.00 -94.00  30.00   54
 21  \w     74.00 109.00   0.50   16.00    --  111.00-110.00  91.66   70
 22  \w     67.00 176.00   0.50   16.00    --  111.00  15.00 120.00  218
 23  \w    100.00 149.00   0.50   16.00    --  111.00 125.00 150.00   98
 24  \w     30.00  67.00   0.50   16.00    --  111.00 -94.00 150.00   74
 25  \w     73.00 105.00   0.50   16.00    --  111.00 -94.00 150.00   64
 26  \w     82.00 108.00   0.50   16.00    --  111.00-104.00 -45.83   52
 27  \w     32.00  57.00   0.50   16.00    --  111.00 -94.00  30.00   50
 28  \w    127.00 156.00   0.50   16.00    --  111.00 -15.00-180.00   58
 29  \w    109.00 141.00   0.50   16.00    --  111.00 -77.00 150.00   64
 30  \w     41.00  48.00   0.50   16.00    --  111.00 -61.00 -30.00   14
;
_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      -0.0361516000
_diffrn_orient_matrix_UB_12      0.1313681000
_diffrn_orient_matrix_UB_13      0.0073368000
_diffrn_orient_matrix_UB_21      -0.0513181000
_diffrn_orient_matrix_UB_22      -0.1020972000
_diffrn_orient_matrix_UB_23      -0.0125407000
_diffrn_orient_matrix_UB_31      0.0170837000
_diffrn_orient_matrix_UB_32      -0.0286126000
_diffrn_orient_matrix_UB_33      0.0780698000
_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  0.0470
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            20527
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.846
_diffrn_reflns_theta_min         3.733
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.447
_exptl_absorpt_correction_T_max  0.907
_exptl_absorpt_correction_T_min  0.772
_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    1.421
_exptl_crystal_description       plate
_exptl_crystal_F_000             1984
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.046
_refine_diff_density_max         0.716
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     286
_refine_ls_number_reflns         4651
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0675P)^2^+2.2554P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1056
_refine_ls_wR_factor_ref         0.1148
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3773
_reflns_number_total             4651
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1724
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_original_cell_volume        4443.34(19)
_cod_database_code               1576799
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H50F6N6O6P2S2
_reflns_odcompleteness_completeness 99.73
_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.a Ternary CH refined with riding coordinates:
 C4(H4), C9(H9), C12(H12)
2.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C17(H17), C18(H18)
2.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,
 H10B,H10C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              34144
_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 1.239
_oxdiff_exptl_absorpt_empirical_full_min 0.723