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_1576800
_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         'C29 H53 N2 O3 P2, C F3 O3 S'
_chemical_formula_sum            'C30 H53 F3 N2 O6 P2 S'
_chemical_formula_weight         688.74
_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             2025-04-10
_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                 94.9020(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.58510(10)
_cell_length_b                   18.8359(2)
_cell_length_c                   17.73090(10)
_cell_measurement_reflns_used    18520
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.5450
_cell_measurement_theta_min      3.4220
_cell_volume                     3522.25(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 1.000
_diffrn_measured_fraction_theta_max 0.988
_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    -74.00 -49.00   0.50    0.50    --  -38.50 131.00  26.00   50
  2  \w    -61.00 -25.00   0.50    0.50    --  -38.50 139.00-158.00   72
  3  \w     63.00  92.00   0.50    0.50    --   42.75-131.00 -44.00   58
  4  \w     51.00 106.00   0.50    0.50    --   42.75-139.00 141.00  110
  5  \w     74.00 122.00   0.50    1.00    --  111.00-139.00 141.00   96
  6  \w     55.00  80.00   0.50    1.00    --  111.00-131.00 -44.00   50
  7  \w    108.00 133.00   0.50    1.00    --  111.00 139.00-158.00   50
  8  \w    116.00 144.00   0.50    1.00    --  111.00 131.00  26.00   56
  9  \w   -111.00 -17.00   0.50    0.50    --  -38.50 -38.00  90.00  188
 10  \w    -90.00 -18.00   0.50    0.50    --  -38.50 -38.00   0.00  144
 11  \w     21.00 115.00   0.50    0.50    --   42.75  38.00   0.00  188
 12  \w    -30.00  65.00   0.50    0.50    --   42.75 -38.00-180.00  190
 13  \w     70.00 129.00   0.50    1.00    --  111.00 -45.00 120.00  118
 14  \w     62.00 111.00   0.50    1.00    --  111.00-125.00-180.00   98
 15  \w     52.00  81.00   0.50    1.00    --  111.00 -61.00 -90.00   58
 16  \w     70.00 107.00   0.50    1.00    --  111.00 -94.00 150.00   74
 17  \w    121.00 149.00   0.50    1.00    --  111.00  77.00 -90.00   56
 18  \w     31.00  86.00   0.50    1.00    --  111.00 -94.00 -60.00  110
 19  \w     94.00 171.00   0.50    1.00    --  111.00  61.00   0.00  154
 20  \w     54.00 112.00   0.50    1.00    --  111.00-125.00  90.00  116
 21  \w     79.00 107.00   0.50    1.00    --  111.00 -94.00-180.00   56
 22  \w     43.00  99.00   0.50    1.00    --  111.00-125.00 150.00  112
 23  \w     79.00 107.00   0.50    1.00    --  111.00 -94.00 -30.00   56
 24  \w     89.00 177.00   0.50    1.00    --  111.00  45.00  90.00  176
 25  \w     75.00 112.00   0.50    1.00    --  111.00-125.00 -90.00   74
 26  \w     89.00 176.00   0.50    1.00    --  111.00  30.00  60.00  174
 27  \w     78.00 105.00   0.50    1.00    --  111.00-125.00-120.00   54
 28  \w     99.00 178.00   0.50    1.00    --  111.00  30.00 150.00  158
 29  \w     30.00  76.00   0.50    1.00    --  111.00 -94.00 -90.00   92
 30  \w     82.00 107.00   0.50    1.00    --  111.00 -94.00 -90.00   50
 31  \w     38.00  83.00   0.50    1.00    --  111.00 -77.00 -30.00   90
 32  \w     88.00 130.00   0.50    1.00    --  111.00 -77.00 -30.00   84
 33  \w     42.00  86.00   0.50    1.00    --  111.00-125.00-150.00   88
 34  \w     89.00 140.00   0.50    1.00    --  111.00  30.00-120.00  102
 35  \w    107.00 138.00   0.50    1.00    --  111.00 -61.00 -90.00   62
 36  \w    145.00 178.00   0.50    1.00    --  111.00  45.00 -30.00   66
 37  \w     66.00 105.00   0.50    1.00    --  111.00 -94.00-120.00   78
 38  \w    100.00 146.00   0.50    1.00    --  111.00 125.00 -90.00   92
 39  \w     87.00 139.00   0.50    1.00    --  111.00  45.00 -30.00  104
;
_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      0.0016419000
_diffrn_orient_matrix_UB_12      0.0807296000
_diffrn_orient_matrix_UB_13      -0.0136184000
_diffrn_orient_matrix_UB_21      0.0376997000
_diffrn_orient_matrix_UB_22      -0.0126460000
_diffrn_orient_matrix_UB_23      -0.0809501000
_diffrn_orient_matrix_UB_31      -0.1411570000
_diffrn_orient_matrix_UB_32      -0.0025404000
_diffrn_orient_matrix_UB_33      -0.0294672000
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            41769
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.981
_diffrn_reflns_theta_min         3.430
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.172
_exptl_absorpt_correction_T_max  0.630
_exptl_absorpt_correction_T_min  0.444
_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    1.299
_exptl_crystal_description       block
_exptl_crystal_F_000             1472
_exptl_crystal_size_max          0.628
_exptl_crystal_size_mid          0.484
_exptl_crystal_size_min          0.346
_refine_diff_density_max         0.408
_refine_diff_density_min         -0.579
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     403
_refine_ls_number_reflns         7369
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0459
_refine_ls_R_factor_gt           0.0431
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0745P)^2^+1.5778P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1160
_refine_ls_wR_factor_ref         0.1189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6805
_reflns_number_total             7369
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1876
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576800
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C30H53F3N2O6P2S
_reflns_odcompleteness_completeness 99.78
_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:
 C4(H4), C9(H9), C12(H12), C18(H18), C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
 C23(H23A,H23B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
  C29(H29A,H29B)
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              67387
_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 1.463
_oxdiff_exptl_absorpt_empirical_full_min 0.550