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_1576795
_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         'C16 H30 N2 P, C F3 O3 S'
_chemical_formula_sum            'C17 H30 F3 N2 O3 P S'
_chemical_formula_weight         430.46
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-18
_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                 100.8860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.54210(10)
_cell_length_b                   20.0160(2)
_cell_length_c                   11.7739(2)
_cell_measurement_reflns_used    9827
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2210
_cell_measurement_theta_min      4.3860
_cell_volume                     2208.29(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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_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    -24.00  45.00   0.50    3.00    --  -38.50   8.00 -16.00  138
  2  \w   -121.00 -16.00   0.50    3.00    --  -38.50  -8.00 169.00  210
  3  \w     73.00 126.00   0.50    3.00    --   42.50   8.00 -16.00  106
  4  \w    137.00 164.00   0.50   12.00    --  111.00   8.00 -16.00   54
  5  \w     99.00 126.00   0.50   12.00    --  111.00   8.00 -16.00   54
  6  \w     38.00 104.00   0.50   12.00    --  111.00  -8.00 169.00  132
  7  \w    -51.00 -24.00   0.50    3.00    --  -38.50 125.00  60.00   54
  8  \w     14.00  81.00   0.50    3.00    --   42.50 -99.00-180.00  134
  9  \w     28.00  79.00   0.50    3.00    --   42.50-125.00  30.00  102
 10  \w     37.00  68.00   0.50    3.00    --   42.50-125.00 -60.00   62
 11  \w     16.00  41.00   0.50    3.00    --   42.50  -8.00 169.00   50
 12  \w     28.00  65.00   0.50    3.00    --   42.50-125.00 120.00   74
 13  \w     54.00  90.00   0.50   12.00    --  111.00 -61.00-150.00   72
 14  \w    109.00 139.00   0.50   12.00    --  111.00 -61.00  30.00   60
 15  \w     81.00 107.00   0.50   12.00    --  111.00 -94.00  30.00   52
 16  \w     86.00 112.00   0.50   12.00    --  111.00-125.00-150.00   52
 17  \w     42.00  86.00   0.50   12.00    --  111.00-125.00  30.00   88
 18  \w     43.00  69.00   0.50   12.00    --  111.00-125.00  60.00   52
 19  \w     37.00 128.00   0.50   12.00    --  111.00 -30.00   0.00  182
 20  \w    115.00 175.00   0.50   12.00    --  111.00  77.00   0.00  120
 21  \w     62.00 134.00   0.50   12.00    --  111.00 -30.00-150.00  144
 22  \w     52.00  86.00   0.50   12.00    --  111.00 -61.00  30.00   68
 23  \w     61.00 111.00   0.50   12.00    --  111.00-125.00 150.00  100
 24  \w    117.00 154.00   0.50   12.00    --  111.00  77.00-180.00   74
 25  \w     81.00 107.00   0.50   12.00    --  111.00 -94.00 -30.00   52
 26  \w     88.00 159.00   0.50   12.00    --  111.00  30.00-180.00  142
 27  \w     40.00  90.00   0.50   12.00    --  111.00 -77.00  30.00  100
 28  \w    106.00 137.00   0.50   12.00    --  111.00 -77.00  30.00   62
 29  \w     75.00 108.00   0.50   12.00    --  111.00-106.00 -19.54   66
 30  \w     44.00 107.00   0.50   12.00    --  111.00 -94.00-180.00  126
 31  \w     87.00 112.00   0.50   12.00    --  111.00-125.00 -60.00   50
 32  \w     76.00 109.00   0.50   12.00    --  111.00-125.00  60.00   66
 33  \w     96.00 173.00   0.50   12.00    --  111.00  15.00 120.00  154
 34  \w     40.00  65.00   0.50   12.00    --  111.00 -94.00  90.00   50
 35  \w     44.00  78.00   0.50   12.00    --  111.00 -77.00-150.00   68
 36  \w     42.00  67.00   0.50   12.00    --  111.00-125.00 -60.00   50
 37  \w     57.00 110.00   0.50   12.00    --  111.00-125.00 -30.00  106
 38  \w    106.00 136.00   0.50   12.00    --  111.00 -61.00-150.00   60
 39  \w     33.00  82.00   0.50   12.00    --  111.00 -94.00-150.00   98
 40  \w     82.00 107.00   0.50   12.00    --  111.00 -94.00 120.00   50
 41  \w    120.00 145.00   0.50   12.00    --  111.00 125.00-120.00   50
 42  \w     30.00  60.00   0.50   12.00    --  111.00 -94.00  30.00   60
;
_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      -0.0182378000
_diffrn_orient_matrix_UB_12      0.0018498000
_diffrn_orient_matrix_UB_13      -0.1328497000
_diffrn_orient_matrix_UB_21      -0.1624866000
_diffrn_orient_matrix_UB_22      0.0078319000
_diffrn_orient_matrix_UB_23      -0.0100884000
_diffrn_orient_matrix_UB_31      0.0168880000
_diffrn_orient_matrix_UB_32      0.0765230000
_diffrn_orient_matrix_UB_33      0.0042862000
_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  0.0387
_diffrn_reflns_av_unetI/netI     0.0255
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            25584
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.743
_diffrn_reflns_theta_min         4.416
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.382
_exptl_absorpt_correction_T_max  0.895
_exptl_absorpt_correction_T_min  0.813
_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    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.115
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.064
_refine_diff_density_max         0.353
_refine_diff_density_min         -0.428
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         4624
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0501
_refine_ls_R_factor_gt           0.0457
_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^)+(0.0412P)^2^+2.5218P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1156
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4206
_reflns_number_total             4624
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1734
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576795
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C17H30F3N2O3PS
_reflns_odcompleteness_completeness 99.94
_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)
2.b 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), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C16(H16A,H16B,H16C)
;
_shelx_res_checksum              1319
_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 1.602
_oxdiff_exptl_absorpt_empirical_full_min 0.821