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_1576791
_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         'C33 H54 N4 O3 P2, 2(C F3 O3 S)'
_chemical_formula_sum            'C35 H54 F6 N4 O9 P2 S2'
_chemical_formula_weight         914.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-16
_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                 90.0260(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.49620(10)
_cell_length_b                   16.7168(2)
_cell_length_c                   14.43090(10)
_cell_measurement_reflns_used    8970
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      75.3750
_cell_measurement_theta_min      2.6330
_cell_volume                     2532.09(4)
_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      200.00(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 0.989
_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   -111.00 -26.00   0.50    0.50    --  -38.50 -38.00 -90.00  170
  2  \w    -82.00 -14.00   0.50    0.50    --  -38.50 125.00  60.00  136
  3  \w    -38.00  -6.00   0.50    0.50    --  -38.50 125.00 120.00   64
  4  \w    -75.00  39.00   0.50    0.50    --  -38.50  19.00  90.00  228
  5  \w     54.00  90.00   0.50    0.50    --   42.75-125.00   0.00   72
  6  \w     27.00  68.00   0.50    0.50    --   42.75-125.00-120.00   82
  7  \w     47.00 114.00   0.50    2.00    --  111.00 -30.00  90.00  134
  8  \w     42.00  93.00   0.50    2.00    --  111.00-125.00  30.00  102
  9  \w     46.00  87.00   0.50    2.00    --  111.00 -45.00-180.00   82
 10  \w     68.00  95.00   0.50    2.00    --  111.00 -94.00-180.00   54
 11  \w     98.00 143.00   0.50    2.00    --  111.00 125.00  90.00   90
 12  \w     86.00 112.00   0.50    2.00    --  111.00-125.00-150.00   52
 13  \w     47.00  89.00   0.50    2.00    --  111.00 -94.00  30.00   84
 14  \w     32.00 121.00   0.50    2.00    --  111.00 -15.00 150.00  178
 15  \w     98.00 177.00   0.50    2.00    --  111.00 125.00  30.00  158
 16  \w     56.00 135.00   0.50    2.00    --  111.00 -30.00   0.00  158
 17  \w     63.00  90.00   0.50    2.00    --  111.00-125.00 120.00   54
 18  \w     81.00 107.00   0.50    2.00    --  111.00 -94.00-120.00   52
 19  \w     45.00 137.00   0.50    2.00    --  111.00 -61.00  90.00  184
 20  \w     53.00 107.00   0.50    2.00    --  111.00 -94.00 -60.00  108
 21  \w     87.00 172.00   0.50    2.00    --  111.00  30.00 -30.00  170
 22  \w     63.00 107.00   0.50    2.00    --  111.00 -94.00   0.00   88
 23  \w     71.00 133.00   0.50    2.00    --  111.00  15.00  90.00  124
 24  \w    153.00 178.00   0.50    2.00    --  111.00  15.00  90.00   50
 25  \w    122.00 173.00   0.50    2.00    --  111.00  77.00 150.00  102
 26  \w     57.00  84.00   0.50    2.00    --  111.00-125.00   0.00   54
 27  \w     36.00 107.00   0.50    2.00    --  111.00 -94.00  60.00  142
 28  \w     87.00 112.00   0.50    2.00    --  111.00-125.00-180.00   50
 29  \w     75.00 110.00   0.50    2.00    --  111.00-125.00 -90.00   70
 30  \w     57.00 107.00   0.50    2.00    --  111.00 -94.00 120.00  100
;
_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      0.1410594000
_diffrn_orient_matrix_UB_12      0.0024943000
_diffrn_orient_matrix_UB_13      0.0293516000
_diffrn_orient_matrix_UB_21      -0.0082830000
_diffrn_orient_matrix_UB_22      0.0915321000
_diffrn_orient_matrix_UB_23      0.0108755000
_diffrn_orient_matrix_UB_31      -0.0395545000
_diffrn_orient_matrix_UB_32      -0.0105011000
_diffrn_orient_matrix_UB_33      0.1020797000
_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  0.0346
_diffrn_reflns_av_unetI/netI     0.0316
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            25804
_diffrn_reflns_point_group_measured_fraction_full 0.728
_diffrn_reflns_point_group_measured_fraction_max 0.708
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.103
_diffrn_reflns_theta_min         2.643
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.156
_exptl_absorpt_correction_T_max  0.844
_exptl_absorpt_correction_T_min  0.605
_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    1.200
_exptl_crystal_description       block
_exptl_crystal_F_000             960
_exptl_crystal_size_max          0.347
_exptl_crystal_size_mid          0.197
_exptl_crystal_size_min          0.089
_refine_diff_density_max         0.189
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.044
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         7580
_refine_ls_number_restraints     153
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0515
_refine_ls_R_factor_gt           0.0470
_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^)+(0.0972P)^2^+0.0218P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1320
_refine_ls_wR_factor_ref         0.1394
_reflns_Friedel_coverage         0.429
_reflns_Friedel_fraction_full    0.456
_reflns_Friedel_fraction_max     0.426
_reflns_number_gt                6766
_reflns_number_total             7580
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1901
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576791
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C35H54F6N4O9P2S2
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.96(3)
 0.04(3)
2. 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, All C(H,H,H,H,H,H) groups
3. Restrained distances
 P2B-H2B = P2A-H2A
 1.414 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C35A \\sim F6A \\sim F4A \\sim F5A \\sim S2A \\sim O8A \\sim O9A \\sim O7A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O3A \\sim C33A \\sim C32A \\sim C33B \\sim C32B \\sim O3B: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 C35A, F6A, F4A, F5A, S2A, O8A, O9A, O7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H2A)=1-FVAR(1)
 Sof(H2B)=FVAR(1)
 Fixed Sof: P1A(0.5) P2A(0.5) C30A(0.5) C24A(0.5) C25A(0.5) H25A(0.5)
 C26A(0.5) H26A(0.5) C27A(0.5) C28A(0.5) H28A(0.5) C29A(0.5) H29A(0.5) O2A(0.5)
 O1A(0.5) C23A(0.5) H23A(0.5) P1B(0.5) C23B(0.5) H23B(0.5) C24B(0.5) C25B(0.5)
 H25B(0.5) C26B(0.5) H26B(0.5) C27B(0.5) C28B(0.5) H28B(0.5) C29B(0.5)
 H29B(0.5) C30B(0.5) O2B(0.5) O1B(0.5) H31A(0.5) H31B(0.5) H31C(0.5) H31D(0.5)
 H31E(0.5) H31F(0.5) P2B(0.5) C35A(0.5) F6A(0.5) F4A(0.5) F5A(0.5) S2A(0.5)
 O8A(0.5) O9A(0.5) O7A(0.5) F4B(0.5) C35B(0.5) F6B(0.5) F5B(0.5) S2B(0.5)
 O9B(0.5) O7B(0.5) O8B(0.5) O3A(0.5) C33A(0.5) H33A(0.5) H33B(0.5) H33C(0.5)
 C32A(0.5) H32A(0.5) H32B(0.5) C33B(0.5) H33D(0.5) H33E(0.5) H33F(0.5)
 C32B(0.5) H32C(0.5) H32D(0.5) O3B(0.5)
7.a Ternary CH refined with riding coordinates:
 C9(H9), C15(H15), C4(H4), C20(H20), C23A(H23A), C23B(H23B)
7.b Secondary CH2 refined with riding coordinates:
 C32A(H32A,H32B), C32B(H32C,H32D)
7.c Aromatic/amide H refined with riding coordinates:
 C25A(H25A), C26A(H26A), C28A(H28A), C29A(H29A), C25B(H25B), C26B(H26B),
 C28B(H28B), C29B(H29B)
7.d Fitted hexagon refined as free rotating group:
 C24A(C25A,C26A,C27A,C28A,C29A)
7.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C6(H6A,H6B,H6C), C21(H21A,H21B,
 H21C), C11(H11A,H11B,H11C), C17(H17A,H17B,H17C), C8(H8A,H8B,H8C), C7(H7A,H7B,
 H7C), C22(H22A,H22B,H22C), C16(H16A,H16B,H16C), C10(H10A,H10B,H10C), C5(H5A,
 H5B,H5C), C31(H31A,H31B,H31C), C31(H31D,H31E,H31F), C33A(H33A,H33B,H33C),
 C33B(H33D,H33E,H33F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 124 electrons were
found in a volume of 346\%A^3 in 1 void per unit cell.
This is consistent with the presence of 1[C6H4F2] per Asymmetric Unit which account for 116 electrons per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6927
_shelx_fab_checksum              61153
_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 1.573
_oxdiff_exptl_absorpt_empirical_full_min 0.672