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_1576796
_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         'C40 H61 F5 N6 P3, 3(C F3 O3 S), C6 H5 F'
_chemical_formula_sum            'C49 H66 F15 N6 O9 P3 S3'
_chemical_formula_weight         1357.16
_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             2025-12-16
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-20 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.5860(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.82790(10)
_cell_length_b                   15.67600(10)
_cell_length_c                   26.6476(2)
_cell_measurement_reflns_used    25753
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      76.5250
_cell_measurement_theta_min      3.0080
_cell_volume                     6107.54(8)
_computing_cell_refinement       'CrysAlisPro 1.171.44.121a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.118a 64-bit (release 22-07-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.121a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      100.0(2)
_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 0.994
_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    -81.00  -7.00   0.50    2.00    --  -38.50 125.00 -90.00  148
  2  \w    -31.00  -6.00   0.50    2.00    --  -38.50 125.00-120.00   50
  3  \w   -111.00 -16.00   0.50    2.00    --  -38.50 -38.00  90.00  190
  4  \w   -110.00 -22.00   0.50    2.00    --  -38.50 -38.00   0.00  176
  5  \w    -56.00  25.00   0.50    2.00    --  -38.50  57.00-120.00  162
  6  \w     52.00  92.00   0.50    2.00    --   42.75-125.00-180.00   80
  7  \w     42.00  67.00   0.50    8.00    --  111.00-125.00-120.00   50
  8  \w    109.00 162.00   0.50    8.00    --  111.00 125.00  60.00  106
  9  \w     64.00 135.00   0.50    8.00    --  111.00 -30.00   0.00  142
 10  \w     41.00 104.00   0.50    8.00    --  111.00 -45.00 -90.00  126
 11  \w     41.00 114.00   0.50    8.00    --  111.00 -45.00 150.00  146
 12  \w    143.00 173.00   0.50    8.00    --  111.00  77.00 -60.00   60
 13  \w     79.00 109.00   0.50    8.00    --  111.00-125.00-120.00   60
 14  \w     43.00 106.00   0.50    8.00    --  111.00 -94.00 -60.00  126
 15  \w     53.00 110.00   0.50    8.00    --  111.00-125.00-180.00  114
 16  \w     30.00 107.00   0.50    8.00    --  111.00 -94.00  30.00  154
 17  \w     44.00 126.00   0.50    8.00    --  111.00 -45.00   0.00  164
 18  \w     57.00 107.00   0.50    8.00    --  111.00 -94.00-180.00  100
 19  \w     66.00  96.00   0.50    8.00    --  111.00 -94.00   0.00   60
 20  \w    104.00 177.00   0.50    8.00    --  111.00  30.00-120.00  146
 21  \w     72.00 123.00   0.50    8.00    --  111.00  15.00  90.00  102
 22  \w    151.00 178.00   0.50    8.00    --  111.00  15.00  90.00   54
 23  \w     89.00 134.00   0.50    8.00    --  111.00  30.00 -60.00   90
 24  \w    145.00 178.00   0.50    8.00    --  111.00  30.00 -60.00   66
 25  \w     73.00 107.00   0.50    8.00    --  111.00 -94.00 120.00   68
 26  \w     80.00 112.00   0.50    8.00    --  111.00-125.00  90.00   64
 27  \w     82.00 107.00   0.50    8.00    --  111.00 -94.00 -30.00   50
 28  \w     80.00 107.00   0.50    8.00    --  111.00 -94.00-120.00   54
 29  \w     54.00  81.00   0.50    8.00    --  111.00-125.00  30.00   54
 30  \w     79.00 106.00   0.50    8.00    --  111.00 -94.00-150.00   54
 31  \w     66.00  93.00   0.50    8.00    --  111.00 -94.00  90.00   54
 32  \w     90.00 172.00   0.50    8.00    --  111.00  30.00   0.00  164
 33  \w    110.00 137.00   0.50    8.00    --  111.00 -77.00 150.00   54
 34  \w     82.00 107.00   0.50    8.00    --  111.00 -94.00  60.00   50
 35  \w    140.00 173.00   0.50    8.00    --  111.00 125.00  30.00   66
 36  \w     39.00  67.00   0.50    8.00    --  111.00 -77.00 150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1043237000
_diffrn_orient_matrix_UB_12      -0.0046004000
_diffrn_orient_matrix_UB_13      0.0174059000
_diffrn_orient_matrix_UB_21      -0.0122312000
_diffrn_orient_matrix_UB_22      0.0272209000
_diffrn_orient_matrix_UB_23      0.0540088000
_diffrn_orient_matrix_UB_31      -0.0085835000
_diffrn_orient_matrix_UB_32      -0.0942910000
_diffrn_orient_matrix_UB_33      0.0147658000
_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  0.0370
_diffrn_reflns_av_unetI/netI     0.0252
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            66528
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.759
_diffrn_reflns_theta_min         3.022
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.767
_exptl_absorpt_correction_T_max  0.926
_exptl_absorpt_correction_T_min  0.769
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.121a (Rigaku Oxford Diffraction, 2025)
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    1.476
_exptl_crystal_description       plank
_exptl_crystal_F_000             2808
_exptl_crystal_size_max          0.398
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.072
_refine_diff_density_max         0.990
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     877
_refine_ls_number_reflns         12803
_refine_ls_number_restraints     481
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0654
_refine_ls_R_factor_gt           0.0575
_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^)+(0.1063P)^2^+5.7923P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1668
_refine_ls_wR_factor_ref         0.1766
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10983
_reflns_number_total             12803
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw2009
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576796
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C49H66F15N6O9P3S3
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name ROY15122025Cu.xpar
_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. Uiso/Uaniso restraints and constraints
F15A \\sim C44A \\sim C45A \\sim C46A \\sim C47A \\sim C48A \\sim C49A \\sim
F15C \\sim C44C \\sim C45C \\sim C46C \\sim C47C \\sim C48C \\sim C49C \\sim
F15B \\sim C45B \\sim C46B \\sim C47B \\sim C48B \\sim C49B \\sim C44B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 1*[Sof(F15A)+Sof(C44A)+Sof(C45A)+Sof(H45A)+Sof(C46A)+Sof(H46A)+Sof(C47A)+
 Sof(H47A)+Sof(C48A)+Sof(H48A)+Sof(C49A)+Sof(H49A)]+1*[Sof(F15C)+Sof(C44C)+
 Sof(C45C)+Sof(H45C)+Sof(C46C)+Sof(H46C)+Sof(C47C)+Sof(H47C)+Sof(C48C)+
 Sof(H48C)+Sof(C49C)+Sof(H49C)]+1*[Sof(F15B)+Sof(C45B)+Sof(H45B)+Sof(C46B)+
 Sof(H46B)+Sof(C47B)+Sof(H47B)+Sof(C48B)+Sof(H48B)+Sof(C49B)+Sof(H49B)+
 Sof(C44B)]=1 with esd of 0
 Sof(F15A)=Sof(C44A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=
 Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=Sof(H49A)=FVAR(1)
 Sof(F15B)=Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46B)=Sof(C47B)=Sof(H47B)=
 Sof(C48B)=Sof(H48B)=Sof(C49B)=Sof(H49B)=Sof(C44B)=FVAR(2)
 Sof(F15C)=Sof(C44C)=Sof(C45C)=Sof(H45C)=Sof(C46C)=Sof(H46C)=Sof(C47C)=
 Sof(H47C)=Sof(C48C)=Sof(H48C)=Sof(C49C)=Sof(H49C)=FVAR(3)
4.a Ternary CH refined with riding coordinates:
 C6(H6), C9(H9), C17(H17), C20(H20), C28(H28), C31(H31), C34(H34)
4.b Aromatic/amide H refined with riding coordinates:
 C45A(H45A), C46A(H46A), C47A(H47A), C48A(H48A), C49A(H49A), C45C(H45C),
 C46C(H46C), C47C(H47C), C48C(H48C), C49C(H49C), C45B(H45B), C46B(H46B),
 C47B(H47B), C48B(H48B), C49B(H49B)
4.c Fitted hexagon refined as free rotating group:
 C44A(C45A,C46A,C47A,C48A,C49A), C44C(C45C,C46C,C47C,C48C,C49C), C45B(C46B,
 C47B,C48B,C49B,C44B)
4.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), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              42069
_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 1.383
_oxdiff_exptl_absorpt_empirical_full_min 0.632