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_1576801
_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         'C F3 O3 S, C24 H35 N3 O2 P'
_chemical_formula_sum            'C25 H35 F3 N3 O5 P S'
_chemical_formula_weight         577.59
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-03-11
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.5490(2)
_cell_length_b                   8.46980(10)
_cell_length_c                   15.24110(10)
_cell_measurement_reflns_used    16298
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      75.9730
_cell_measurement_theta_min      4.1080
_cell_volume                     2781.74(5)
_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      100.01(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 0.995
_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     20.00 115.00   0.50    1.50    --   42.50  38.00-120.00  190
  2  \w     73.00  98.00   0.50    1.50    --   42.50-125.00 -90.00   50
  3  \w    -11.00  56.00   0.50    1.50    --   42.50 -77.00 -90.00  134
  4  \w     32.00  95.00   0.50    1.50    --   42.50-125.00-120.00  126
  5  \w    -28.00  68.00   0.50    1.50    --   42.50 -57.00 -30.00  192
  6  \w     16.00 109.00   0.50    1.50    --   42.50  57.00 120.00  186
  7  \w     45.00 111.00   0.50    6.00    --  111.00 -45.00 120.00  132
  8  \w     40.00  85.00   0.50    6.00    --  111.00 -94.00  30.00   90
  9  \w     34.00 131.00   0.50    6.00    --  111.00 -15.00 -90.00  194
 10  \w     66.00 126.00   0.50    6.00    --  111.00  15.00-150.00  120
 11  \w     83.00 112.00   0.50    6.00    --  111.00-125.00 -90.00   58
 12  \w     54.00  81.00   0.50    6.00    --  111.00 -30.00  60.00   54
 13  \w    110.00 135.00   0.50    6.00    --  111.00 -30.00  60.00   50
 14  \w    139.00 167.00   0.50    6.00    --  111.00  45.00  60.00   56
 15  \w     38.00  91.00   0.50    6.00    --  111.00-114.00 -74.33  106
 16  \w     33.00 102.00   0.50    6.00    --  111.00 -94.00 -30.00  138
 17  \w     65.00 112.00   0.50    6.00    --  111.00-125.00 150.00   94
 18  \w     96.00 125.00   0.50    6.00    --  111.00 -45.00-120.00   58
 19  \w     49.00 137.00   0.50    6.00    --  111.00 -61.00  30.00  176
 20  \w     56.00  83.00   0.50    6.00    --  111.00 -45.00-120.00   54
 21  \w     93.00 178.00   0.50    6.00    --  111.00  45.00  90.00  170
 22  \w    134.00 159.00   0.50    6.00    --  111.00  15.00-150.00   50
 23  \w     36.00 107.00   0.50    6.00    --  111.00 -94.00  60.00  142
 24  \w     62.00 107.00   0.50    6.00    --  111.00 -94.00   0.00   90
 25  \w    113.00 140.00   0.50    6.00    --  111.00 125.00-120.00   54
 26  \w    105.00 177.00   0.50    6.00    --  111.00  77.00-150.00  144
 27  \w     83.00 138.00   0.50    6.00    --  111.00 -61.00 120.00  110
 28  \w     72.00 107.00   0.50    6.00    --  111.00 -94.00 150.00   70
 29  \w     82.00 107.00   0.50    6.00    --  111.00 -94.00 120.00   50
 30  \w     39.00 110.00   0.50    6.00    --  111.00-115.00 -49.90  142
;
_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      -0.0696495000
_diffrn_orient_matrix_UB_12      -0.0234636000
_diffrn_orient_matrix_UB_13      0.0186660000
_diffrn_orient_matrix_UB_21      -0.0161425000
_diffrn_orient_matrix_UB_22      0.0946723000
_diffrn_orient_matrix_UB_23      -0.0832593000
_diffrn_orient_matrix_UB_31      0.0007540000
_diffrn_orient_matrix_UB_32      -0.1534857000
_diffrn_orient_matrix_UB_33      -0.0541934000
_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  0.0256
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            28113
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.835
_diffrn_reflns_theta_min         4.103
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.107
_exptl_absorpt_correction_T_max  0.872
_exptl_absorpt_correction_T_min  0.734
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             1216
_exptl_crystal_size_max          0.222
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.499
_refine_diff_density_min         -0.197
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 2590 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.025(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         5720
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0279
_refine_ls_R_factor_gt           0.0275
_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^)+(0.0441P)^2^+0.6766P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0737
_refine_ls_wR_factor_ref         0.0741
_reflns_Friedel_coverage         0.883
_reflns_Friedel_fraction_full    0.966
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                5648
_reflns_number_total             5720
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1351
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576801
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C25H35F3N3O5PS
_reflns_odcompleteness_completeness 99.97
_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.a Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C15(H15A,H15B)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C21(H21), C23(H23), C24(H24)
2.d 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), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_shelx_res_checksum              26493
_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 1.195
_oxdiff_exptl_absorpt_empirical_full_min 0.817