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_1576792
_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
'C36 H50 N6 O4 P2, 2(C F3 O3 S), C2 H3 N, C4 H10 O'
_chemical_formula_sum            'C44 H63 F6 N7 O11 P2 S2'
_chemical_formula_weight         1106.07
_space_group_crystal_system      hexagonal
_space_group_IT_number           170
_space_group_name_Hall           'P 65'
_space_group_name_H-M_alt        'P 65'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-19
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2025-12-20 deposited with the CCDC.	2025-12-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   13.7455(3)
_cell_length_b                   13.7455(3)
_cell_length_c                   48.9066(10)
_cell_measurement_reflns_used    8406
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      69.7940
_cell_measurement_theta_min      3.7120
_cell_volume                     8002.4(3)
_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      99.98(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 1.000
_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   -108.00 -83.00   0.50    7.50    --  -38.50-158.00 -66.00   50
  2  \w    -63.00  -1.00   0.50    7.50    --  -38.50 118.00 172.00  124
  3  \w     58.00  83.00   0.50    7.50    --   42.50-158.00 -66.00   50
  4  \w     94.00 119.00   0.50   30.00    --  111.00 158.00 -33.00   50
  5  \w     66.00  91.00   0.50   30.00    --  111.00-158.00 -66.00   50
  6  \w     50.00  75.00   0.50   30.00    --  111.00-118.00  86.00   50
  7  \w    -55.00  33.00   0.50    7.50    --  -38.50  38.00   0.00  176
  8  \w    -58.00  31.00   0.50    7.50    --  -38.50  38.00-180.00  178
  9  \w    114.00 140.00   0.50   30.00    --  111.00  30.00  90.00   52
 10  \w     52.00 112.00   0.50   30.00    --  111.00-125.00 -90.00  120
 11  \w     78.00 103.00   0.50   30.00    --  111.00-125.00 -60.00   50
 12  \w     44.00 109.00   0.50   30.00    --  111.00-125.00 150.00  130
 13  \w    140.00 177.00   0.50   30.00    --  111.00  45.00  90.00   74
 14  \w     99.00 130.00   0.50   30.00    --  111.00  45.00  90.00   62
 15  \w    108.00 140.00   0.50   30.00    --  111.00  45.00 -90.00   64
 16  \w    103.00 177.00   0.50   30.00    --  111.00  77.00-150.00  148
 17  \w     88.00 142.00   0.50   30.00    --  111.00  45.00 -60.00  108
 18  \w     42.00 104.00   0.50   30.00    --  111.00-125.00 -30.00  124
;
_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      0.0837040000
_diffrn_orient_matrix_UB_12      0.0898372000
_diffrn_orient_matrix_UB_13      0.0199072000
_diffrn_orient_matrix_UB_21      0.0541091000
_diffrn_orient_matrix_UB_22      0.0822451000
_diffrn_orient_matrix_UB_23      -0.0240166000
_diffrn_orient_matrix_UB_31      -0.0826172000
_diffrn_orient_matrix_UB_32      0.0435634000
_diffrn_orient_matrix_UB_33      0.0043878000
_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  0.0557
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       58
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            35270
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.209
_diffrn_reflns_theta_min         3.713
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.192
_exptl_absorpt_correction_T_max  0.933
_exptl_absorpt_correction_T_min  0.698
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       needle
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.364
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.037
_refine_diff_density_max         0.439
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 3143 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.011(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     713
_refine_ls_number_reflns         9735
_refine_ls_number_restraints     397
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0748
_refine_ls_R_factor_gt           0.0613
_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^)+(0.0882P)^2^+2.4033P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1664
_reflns_Friedel_coverage         0.968
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                8107
_reflns_number_total             9735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1544
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_original_cell_volume        8002.4(4)
_cod_database_code               1576792
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C44H62F6N7O11P2S2
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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. Uiso/Uaniso restraints and constraints
S2A \\sim F4A \\sim F5A \\sim F6A \\sim O8A \\sim O9A \\sim O10A \\sim C38A
\\sim S2B \\sim F4B \\sim F5B \\sim F6B \\sim O8B \\sim O9B \\sim O10B \\sim
C38B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
N4 \\sim C12 \\sim N3 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim
C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C1 \\sim N2 \\sim C2 \\sim C3
\\sim N1 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim
C11: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Sof(S2B)=Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(O8B)=Sof(O9B)=Sof(O10B)=Sof(C38B)=1-
 FVAR(1)
 Sof(S2A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O8A)=Sof(O9A)=Sof(O10A)=Sof(C38A)=
 FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C4(H4), C9(H9), C15(H15), C20(H20), C23(H23)
4.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C42(H42A,H42B), C43(H43A,H43B)
4.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C35(H35), C36(H36), C32(H32), C31(H31), C29(H29), C28(H28)
4.d Fitted hexagon refined as free rotating group:
 C24(C33,C34,C35,C36,C25), C27(C32,C31,C30,C29,C28)
4.e 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), C39(H39A,H39B,H39C), C41(H41A,H41B,H41C), C44(H44A,H44B,H44C)
;
_shelx_res_checksum              65231
_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 1.819
_oxdiff_exptl_absorpt_empirical_full_min 0.594