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_1576793
_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         'C38 H50 N6 P2, 2(C F3 O3 S), C2 H3 N'
_chemical_formula_sum            'C42 H53 F6 N7 O6 P2 S2'
_chemical_formula_weight         991.97
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-09
_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                94.291(2)
_cell_angle_beta                 97.156(3)
_cell_angle_gamma                90.210(3)
_cell_formula_units_Z            2
_cell_length_a                   10.2822(3)
_cell_length_b                   13.2602(4)
_cell_length_c                   17.8827(5)
_cell_measurement_reflns_used    11308
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.0240
_cell_measurement_theta_min      2.4900
_cell_volume                     2412.22(12)
_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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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   -110.00 -15.00   0.50    1.00    --  -38.50 -41.00-172.00  190
  2  \w     -1.00  32.00   0.50    1.00    --  -38.50  41.00 -20.00   66
  3  \w    -39.00 -12.00   0.50    1.00    --  -38.50  41.00 -20.00   54
  4  \w     22.00 111.00   0.50    1.00    --   42.75  41.00 -20.00  178
  5  \w    114.00 168.00   0.50    4.00    --  111.00  41.00 -20.00  108
  6  \w     65.00  92.00   0.50    4.00    --  111.00 -41.00-172.00   54
  7  \w    -82.00 -10.00   0.50    1.00    --  -38.50 125.00  90.00  144
  8  \w    -33.00  -8.00   0.50    1.00    --  -38.50 125.00   0.00   50
  9  \w     10.00  82.00   0.50    1.00    --   42.75 -99.00   0.00  144
 10  \w      9.00  36.00   0.50    1.00    --   42.75 -99.00  90.00   54
 11  \w     18.00  45.00   0.50    1.00    --   42.75 -41.00-172.00   54
 12  \w     54.00 103.00   0.50    1.00    --   42.75  38.00 -90.00   98
 13  \w     39.00  66.00   0.50    4.00    --  111.00 -97.00-141.08   54
 14  \w     87.00 177.00   0.50    4.00    --  111.00  30.00 -90.00  180
 15  \w    143.00 168.00   0.50    4.00    --  111.00 125.00-150.00   50
 16  \w     97.00 178.00   0.50    4.00    --  111.00  45.00-150.00  162
 17  \w    146.00 173.00   0.50    4.00    --  111.00  77.00 -60.00   54
 18  \w     42.00 110.00   0.50    4.00    --  111.00-125.00 -30.00  136
 19  \w     75.00 107.00   0.50    4.00    --  111.00 -94.00  60.00   64
 20  \w     89.00 139.00   0.50    4.00    --  111.00 -61.00  60.00  100
 21  \w     47.00  91.00   0.50    4.00    --  111.00-125.00  30.00   88
 22  \w    102.00 129.00   0.50    4.00    --  111.00 125.00 150.00   54
 23  \w     41.00 102.00   0.50    4.00    --  111.00-125.00  60.00  122
 24  \w     38.00  96.00   0.50    4.00    --  111.00 -77.00-150.00  116
 25  \w    129.00 178.00   0.50    4.00    --  111.00  77.00  90.00   98
 26  \w     77.00 107.00   0.50    4.00    --  111.00 -94.00-180.00   60
 27  \w     79.00 112.00   0.50    4.00    --  111.00-125.00 150.00   66
 28  \w     41.00 132.00   0.50    4.00    --  111.00 -45.00  30.00  182
 29  \w    103.00 178.00   0.50    4.00    --  111.00  30.00 150.00  150
 30  \w     32.00  58.00   0.50    4.00    --  111.00 -94.00 -60.00   52
 31  \w     66.00 107.00   0.50    4.00    --  111.00 -94.00 -60.00   82
 32  \w     82.00 109.00   0.50    4.00    --  111.00 -61.00-150.00   54
 33  \w     43.00 112.00   0.50    4.00    --  111.00-125.00  90.00  138
 34  \w     67.00 107.00   0.50    4.00    --  111.00 -97.00-141.08   80
 35  \w     76.00 106.00   0.50    4.00    --  111.00 -94.00 150.00   60
 36  \w     55.00 107.00   0.50    4.00    --  111.00 -94.00 -30.00  104
 37  \w    114.00 139.00   0.50    4.00    --  111.00 125.00-150.00   50
;
_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      0.0456442000
_diffrn_orient_matrix_UB_12      0.1097335000
_diffrn_orient_matrix_UB_13      -0.0053092000
_diffrn_orient_matrix_UB_21      0.1103002000
_diffrn_orient_matrix_UB_22      -0.0388013000
_diffrn_orient_matrix_UB_23      -0.0451570000
_diffrn_orient_matrix_UB_31      -0.0925029000
_diffrn_orient_matrix_UB_32      0.0053827000
_diffrn_orient_matrix_UB_33      -0.0742618000
_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  0.0261
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            26815
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.734
_diffrn_reflns_theta_min         2.497
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.283
_exptl_absorpt_correction_T_max  0.903
_exptl_absorpt_correction_T_min  0.687
_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    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             1036
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.179
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.819
_refine_diff_density_min         -0.473
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     772
_refine_ls_number_reflns         9990
_refine_ls_number_restraints     677
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0454
_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^)+(0.0688P)^2^+1.3219P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1205
_refine_ls_wR_factor_ref         0.1260
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8795
_reflns_number_total             9990
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1725
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576793
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C42H53F6N7O6P2S2
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 S2A-C40A \\sim S2B-C40B \\sim S2C-C40C
 with sigma of 0.02
 F5C-C40C \\sim F6C-C40C \\sim F4C-C40C \\sim F4B-C40B \\sim F4A-C40A \\sim
F5B-C40B \\sim F5A-C40A ~
 F6A-C40A \\sim F6B-C40B
 with sigma of 0.02
 S2C-O5C \\sim S2C-O6C \\sim S2B-O8A \\sim S2A-O8 \\sim S2B-O9A \\sim S2C-O4C
\\sim S2B-O7A \\sim S2A-O7 ~
 S2A-O9
 with sigma of 0.02
 N7B-C42B \\sim N7A-C42A
 with sigma of 0.02
 C41B-C42B \\sim C41A-C42A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S2A \\sim F4A \\sim F5A \\sim F6A \\sim O7 \\sim O8 \\sim O9 \\sim C40A \\sim
S2C \\sim O4C \\sim F4C \\sim O5C \\sim F5C \\sim F6C \\sim O6C \\sim C40C
\\sim S2B \\sim F4B \\sim F5B \\sim F6B \\sim O7A \\sim O8A \\sim O9A \\sim
C40B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
N7B \\sim C41B \\sim C42B \\sim N7A \\sim C41A \\sim C42A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C41B) \\sim Ueq, Uanis(N7B) \\sim Ueq, Uanis(C42B) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O5C) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Others
 Sof(N7B)=Sof(C41B)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42B)=1-FVAR(1)
 Sof(N7A)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42A)=FVAR(1)
 Fixed Sof: S2A(0.525) F4A(0.525) F5A(0.525) F6A(0.525) O7(0.525) O8(0.525)
 O9(0.525) C40A(0.525) S2C(0.05) O4C(0.05) F4C(0.05) O5C(0.05) F5C(0.05)
 F6C(0.05) O6C(0.05) C40C(0.05) S2B(0.425) F4B(0.425) F5B(0.425) F6B(0.425)
 O7A(0.425) O8A(0.425) O9A(0.425) C40B(0.425)
5.a Ternary CH refined with riding coordinates:
 C4(H4), C9(H9), C15(H15), C20(H20), C26(H26)
5.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B)
5.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C30(H30), C33(H33), C34(H34), C36(H36), C37(H37)
5.d 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), C41B(H41A,H41B,H41C), C41A(H41D,H41E,H41F)
;
_shelx_res_checksum              1742
_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 1.213
_oxdiff_exptl_absorpt_empirical_full_min 0.820