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_1576804
_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
'2(C9 H10.5 F2.5 N P0.5), 2(C0.5 F1.5 O1.5 S0.5)'
_chemical_formula_sum            'C19 H21 F8 N2 O3 P S'
_chemical_formula_weight         540.41
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-08-28
_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                 92.044(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   9.6269(6)
_cell_length_b                   26.2948(18)
_cell_length_c                   18.1460(13)
_cell_measurement_reflns_used    5263
_cell_measurement_temperature    99.94(13)
_cell_measurement_theta_max      67.0960
_cell_measurement_theta_min      2.9470
_cell_volume                     4590.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      99.94(13)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.987
_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   -109.00 -18.00   0.50   10.50    --  -38.50 -62.00  95.00  182
  2  \w    -66.00  30.00   0.50   10.50    --  -38.50  62.00-127.00  192
  3  \w     -3.00  22.00   0.50   10.50    --   42.50 -62.00  95.00   50
  4  \w     49.00 111.00   0.50   10.50    --   42.50  62.00-127.00  124
  5  \w     87.00 119.00   0.50   42.00    --  111.00  62.00-127.00   64
  6  \w     48.00 132.00   0.50   42.00    --  111.00 -62.00  95.00  168
  7  \w     34.00  96.00   0.50   10.50    --   42.50-125.00  60.00  124
  8  \w      6.00  68.00   0.50   10.50    --   42.50 -99.00 -60.00  124
  9  \w     50.00  95.00   0.50   42.00    --  111.00 -94.00-180.00   90
 10  \w     38.00 104.00   0.50   42.00    --  111.00 -94.00 -30.00  132
 11  \w    103.00 145.00   0.50   42.00    --  111.00  77.00 120.00   84
 12  \w    127.00 178.00   0.50   42.00    --  111.00 125.00-180.00  102
 13  \w    104.00 132.00   0.50   42.00    --  111.00  77.00 150.00   56
 14  \w    133.00 161.00   0.50   42.00    --  111.00  61.00 -90.00   56
 15  \w    139.00 175.00   0.50   42.00    --  111.00  77.00 150.00   72
 16  \w    104.00 176.00   0.50   42.00    --  111.00  77.00-120.00  144
 17  \w    111.00 175.00   0.50   42.00    --  111.00  77.00-180.00  128
 18  \w     39.00 112.00   0.50   42.00    --  111.00-125.00 -90.00  146
 19  \w     61.00 107.00   0.50   42.00    --  111.00 -94.00   0.00   92
 20  \w     83.00 111.00   0.50   42.00    --  111.00  61.00 -90.00   56
 21  \w     98.00 177.00   0.50   42.00    --  111.00  30.00 150.00  158
;
_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      0.0195827000
_diffrn_orient_matrix_UB_12      -0.0409362000
_diffrn_orient_matrix_UB_13      0.0601569000
_diffrn_orient_matrix_UB_21      -0.1464742000
_diffrn_orient_matrix_UB_22      0.0114392000
_diffrn_orient_matrix_UB_23      0.0274073000
_diffrn_orient_matrix_UB_31      -0.0620220000
_diffrn_orient_matrix_UB_32      -0.0402766000
_diffrn_orient_matrix_UB_33      -0.0533085000
_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  0.0519
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            25476
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.248
_diffrn_reflns_theta_min         2.960
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.756
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.704
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.564
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2208
_exptl_crystal_size_max          0.162
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.594
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     809
_refine_ls_number_reflns         8307
_refine_ls_number_restraints     505
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0989
_refine_ls_R_factor_gt           0.0708
_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^)+(0.0638P)^2^+9.7495P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1626
_refine_ls_wR_factor_ref         0.1788
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5936
_reflns_number_total             8307
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1430
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576804
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C19H21F8N2O3PS
_shelx_estimated_absorpt_t_max   0.868
_shelx_estimated_absorpt_t_min   0.664
_reflns_odcompleteness_completeness 97.79
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 P2A-C30 \\sim P2B-C30
 with sigma of 0.02
 P2A-C12 \\sim P2B-C12
 with sigma of 0.02
 N4-C20A \\sim N4-C20B
 with sigma of 0.02
 C22-C20A \\sim C22-C20B
 with sigma of 0.02
 C21-C20A \\sim C21-C20B
 with sigma of 0.02
 S2A-O5A \\sim S2B-O5B
 with sigma of 0.02
 S2A-O4A \\sim S2B-O6B
 with sigma of 0.02
 S2A-O6A \\sim S2B-O4B
 with sigma of 0.02
 S2A-C38A \\sim S2B-C38B
 with sigma of 0.02
 F16A-C38A \\sim F16B-C38B
 with sigma of 0.02
 F15A-C38A \\sim F14B-C38B
 with sigma of 0.02
 F14A-C38A \\sim F15B-C38B
 with sigma of 0.02
 S2A-F16A \\sim S2B-F16B
 with sigma of 0.04
 S2A-F15A \\sim S2B-F14B
 with sigma of 0.04
 S2A-F14A \\sim S2B-F15B
 with sigma of 0.04
 F16A-F15A \\sim F16B-F14B
 with sigma of 0.04
 F16A-F14A \\sim F16B-F15B
 with sigma of 0.04
 F15A-F14A \\sim F14B-F15B
 with sigma of 0.04
 O5A-O4A \\sim O5B-O6B
 with sigma of 0.04
 O5A-O6A \\sim O5B-O4B
 with sigma of 0.04
 O5A-C38A \\sim O5B-C38B
 with sigma of 0.04
 O4A-O6A \\sim O6B-O4B
 with sigma of 0.04
 O4A-C38A \\sim O6B-C38B
 with sigma of 0.04
 O6A-C38A \\sim O4B-C38B
 with sigma of 0.04
 S1A-O2A \\sim S1B-O3B
 with sigma of 0.02
 S1A-O3A \\sim S1B-O1B
 with sigma of 0.02
 S1A-O1A \\sim S1B-O2B
 with sigma of 0.02
 S1A-C37A \\sim S1B-C37B
 with sigma of 0.02
 F13A-C37A \\sim F13B-C37B
 with sigma of 0.02
 F11A-C37A \\sim F11B-C37B
 with sigma of 0.02
 F12A-C37A \\sim F12B-C37B
 with sigma of 0.02
 S1A-F13A \\sim S1B-F13B
 with sigma of 0.04
 S1A-F11A \\sim S1B-F11B
 with sigma of 0.04
 S1A-F12A \\sim S1B-F12B
 with sigma of 0.04
 F13A-F11A \\sim F13B-F11B
 with sigma of 0.04
 F13A-F12A \\sim F13B-F12B
 with sigma of 0.04
 O2A-O3A \\sim O3B-O1B
 with sigma of 0.04
 O2A-O1A \\sim O3B-O2B
 with sigma of 0.04
 O2A-C37A \\sim O3B-C37B
 with sigma of 0.04
 F11A-F12A \\sim F11B-F12B
 with sigma of 0.04
 O3A-O1A \\sim O1B-O2B
 with sigma of 0.04
 O3A-C37A \\sim O1B-C37B
 with sigma of 0.04
 O1A-C37A \\sim O2B-C37B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
S2A \\sim F14A \\sim F15A \\sim F16A \\sim O4A \\sim O5A \\sim O6A \\sim C38A
\\sim S2B \\sim F14B \\sim F15B \\sim F16B \\sim O4B \\sim O5B \\sim O6B \\sim
C38B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
S1A \\sim F11A \\sim F12A \\sim F13A \\sim O1A \\sim O2A \\sim O3A \\sim C37A
\\sim S1B \\sim F11B \\sim F12B \\sim F13B \\sim O1B \\sim O2B \\sim O3B \\sim
C37B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
4. Others
 Sof(P2B)=1-FVAR(1)
 Sof(P2A)=FVAR(1)
 Sof(H21D)=Sof(H21E)=Sof(H21F)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C20B)=
 Sof(H20B)=1-FVAR(2)
 Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C20A)=
 Sof(H20A)=FVAR(2)
 Sof(S2B)=Sof(F14B)=Sof(F15B)=Sof(F16B)=Sof(O4B)=Sof(O5B)=Sof(O6B)=Sof(C38B)=1-
 FVAR(3)
 Sof(S2A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(O4A)=Sof(O5A)=Sof(O6A)=Sof(C38A)=
 FVAR(3)
 Sof(S1B)=Sof(F11B)=Sof(F12B)=Sof(F13B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=Sof(C37B)=1-
 FVAR(4)
 Sof(S1A)=Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C37A)=
 FVAR(4)
 Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C9B)=Sof(H9B)=
 1-FVAR(5)
 Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C9A)=Sof(H9A)=
 FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C9A(H9A), C9B(H9B), C13(H13), C20A(H20A), C20B(H20B)
5.b 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), C10(H10D,H10E,H10F), C11(H11A,H11B,H11C), C11(H11D,H11E,H11F),
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C21(H21A,H21B,H21C), C21(H21D,H21E,H21F), C22(H22A,H22B,H22C), C22(H22D,
 H22E,H22F)
;
_shelx_res_checksum              84431
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 2.995
_oxdiff_exptl_absorpt_empirical_full_min 0.672