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_1576797
_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 H45 Br N4 P2, 2(C F3 O3 S), C6 H4 F2'
_chemical_formula_sum            'C37 H49 Br F8 N4 O6 P2 S2'
_chemical_formula_weight         1003.77
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-12
_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                 102.7040(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3115(2)
_cell_length_b                   12.4673(2)
_cell_length_c                   19.7589(3)
_cell_measurement_reflns_used    22900
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4470
_cell_measurement_theta_min      2.4630
_cell_volume                     4400.43(11)
_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    -28.00  32.00   0.50    0.50    --  -38.50  38.00   0.00  120
  2  \w    -85.00 -20.00   0.50    0.50    --  -38.50 125.00 -90.00  130
  3  \w    -58.00 -12.00   0.50    0.50    --  -38.50 125.00   0.00   92
  4  \w   -107.00 -21.00   0.50    0.50    --  -38.50 -38.00-180.00  172
  5  \w   -110.00 -20.00   0.50    0.50    --  -38.50 -38.00  90.00  180
  6  \w     71.00 112.00   0.50    0.50    --   42.50  57.00-120.00   82
  7  \w     52.00  92.00   0.50    0.50    --   42.50-125.00-180.00   80
  8  \w     42.00  98.00   0.50    2.00    --  111.00-125.00 120.00  112
  9  \w     41.00  90.00   0.50    2.00    --  111.00 -45.00 -60.00   98
 10  \w     39.00  96.00   0.50    2.00    --  111.00 -77.00 -90.00  114
 11  \w     80.00 107.00   0.50    2.00    --  111.00 -94.00 -90.00   54
 12  \w     44.00 112.00   0.50    2.00    --  111.00-125.00 -90.00  136
 13  \w     80.00 107.00   0.50    2.00    --  111.00 -94.00 -30.00   54
 14  \w    123.00 177.00   0.50    2.00    --  111.00  77.00  60.00  108
 15  \w     63.00 106.00   0.50    2.00    --  111.00 -94.00  90.00   86
 16  \w     82.00 107.00   0.50    2.00    --  111.00 -94.00-180.00   50
 17  \w     40.00 132.00   0.50    2.00    --  111.00 -45.00  90.00  184
 18  \w     83.00 122.00   0.50    2.00    --  111.00  61.00-120.00   78
 19  \w     69.00 112.00   0.50    2.00    --  111.00-125.00   0.00   86
 20  \w     87.00 178.00   0.50    2.00    --  111.00  45.00 -30.00  182
 21  \w     49.00 112.00   0.50    2.00    --  111.00-125.00 -60.00  126
 22  \w    116.00 164.00   0.50    2.00    --  111.00 125.00 -90.00   96
 23  \w     30.00  60.00   0.50    2.00    --  111.00 -94.00 120.00   60
 24  \w     85.00 112.00   0.50    2.00    --  111.00 -61.00 -90.00   54
 25  \w     42.00  95.00   0.50    2.00    --  111.00 -30.00 -60.00  106
 26  \w     97.00 124.00   0.50    2.00    --  111.00 -30.00 -60.00   54
 27  \w     41.00 112.00   0.50    2.00    --  111.00-125.00  90.00  142
 28  \w    106.00 152.00   0.50    2.00    --  111.00  77.00 150.00   92
 29  \w     79.00 112.00   0.50    2.00    --  111.00-125.00-150.00   66
 30  \w     84.00 112.00   0.50    2.00    --  111.00-125.00 150.00   56
 31  \w    115.00 142.00   0.50    2.00    --  111.00 -77.00 -90.00   54
 32  \w     60.00 107.00   0.50    2.00    --  111.00 -94.00-150.00   94
 33  \w    132.00 171.00   0.50    2.00    --  111.00   0.00 -30.00   78
 34  \w     79.00 107.00   0.50    2.00    --  111.00 -94.00 120.00   56
 35  \w     98.00 161.00   0.50    2.00    --  111.00 125.00-120.00  126
 36  \w     24.00 119.00   0.50    2.00    --  111.00   0.00 -30.00  190
;
_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      -0.0140565000
_diffrn_orient_matrix_UB_12      -0.1186618000
_diffrn_orient_matrix_UB_13      -0.0204566000
_diffrn_orient_matrix_UB_21      -0.0256178000
_diffrn_orient_matrix_UB_22      -0.0211640000
_diffrn_orient_matrix_UB_23      0.0680652000
_diffrn_orient_matrix_UB_31      -0.0810949000
_diffrn_orient_matrix_UB_32      0.0272977000
_diffrn_orient_matrix_UB_33      -0.0365997000
_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  0.0355
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            49573
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.717
_diffrn_reflns_theta_min         2.473
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.578
_exptl_absorpt_correction_T_max  0.851
_exptl_absorpt_correction_T_min  0.499
_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    1.515
_exptl_crystal_description       plate
_exptl_crystal_F_000             2064
_exptl_crystal_size_max          0.285
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.491
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.054
_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     553
_refine_ls_number_reflns         9214
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0271
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0358P)^2^+2.0493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8580
_reflns_number_total             9214
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1899
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576797
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C37H49BrF8N4O6P2S2
_reflns_odcompleteness_completeness 99.99
_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), C15(H15), C20(H20), C23(H23)
2.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C26(H26), C28(H28), C29(H29), C34(H34), C35(H35), C36(H36), C37(H37)
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), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C)
;
_shelx_res_checksum              9083
_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 4.063
_oxdiff_exptl_absorpt_empirical_full_min 0.690