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_1576794
_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
'6(C0.333 F O S0.333), 3(C12 H14 F3.333 N1.333 P0.667)'
_chemical_formula_sum            'C38 H42 F16 N4 O6 P2 S2'
_chemical_formula_weight         1080.81
_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             2021-06-22
_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                 92.3847(3)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   33.48865(11)
_cell_length_b                   18.15171(6)
_cell_length_c                   22.02616(6)
_cell_measurement_reflns_used    66949
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      76.5260
_cell_measurement_theta_min      2.6350
_cell_volume                     13377.58(7)
_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      100.02(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 0.995
_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    -61.00  13.00   0.50    1.50    --  -38.50  99.00 -30.00  148
  2  \w     34.00  82.00   0.50    1.50    --   42.75 -99.00-136.00   96
  3  \w    108.00 141.00   0.50    6.00    --  111.00  99.00 -30.00   66
  4  \w     61.00 107.00   0.50    6.00    --  111.00 -99.00-136.00   92
  5  \w   -108.00 -31.00   0.50    1.50    --  -38.50 -57.00-120.00  154
  6  \w     59.00  86.00   0.50    1.50    --   42.75  38.00   0.00   54
  7  \w     20.00 109.00   0.50    1.50    --   42.75  38.00 120.00  178
  8  \w     20.00 113.00   0.50    1.50    --   42.75  38.00-150.00  186
  9  \w     20.00  56.00   0.50    1.50    --   42.75  38.00   0.00   72
 10  \w     45.00  72.00   0.50    1.50    --   42.75 -99.00  90.00   54
 11  \w     95.00 173.00   0.50    6.00    --  111.00  30.00 150.00  156
 12  \w    143.00 170.00   0.50    6.00    --  111.00 125.00 -90.00   54
 13  \w     88.00 178.00   0.50    6.00    --  111.00  45.00  30.00  180
 14  \w     39.00 112.00   0.50    6.00    --  111.00-125.00-150.00  146
 15  \w    102.00 156.00   0.50    6.00    --  111.00 125.00  60.00  108
 16  \w     34.00 104.00   0.50    6.00    --  111.00 -94.00  60.00  140
 17  \w     41.00  72.00   0.50    6.00    --  111.00 -45.00 -60.00   62
 18  \w     54.00  81.00   0.50    6.00    --  111.00-125.00 -60.00   54
 19  \w     99.00 160.00   0.50    6.00    --  111.00 125.00-150.00  122
 20  \w     98.00 126.00   0.50    6.00    --  111.00 125.00 -90.00   56
 21  \w     45.00 107.00   0.50    6.00    --  111.00 -94.00  30.00  124
 22  \w     33.00 107.00   0.50    6.00    --  111.00 -94.00 120.00  148
 23  \w     35.00 107.00   0.50    6.00    --  111.00 -94.00 -90.00  144
 24  \w     64.00 112.00   0.50    6.00    --  111.00-125.00-120.00   96
 25  \w     66.00 107.00   0.50    6.00    --  111.00 -94.00 -30.00   82
 26  \w     87.00 139.00   0.50    6.00    --  111.00  45.00-150.00  104
 27  \w     97.00 160.00   0.50    6.00    --  111.00  30.00  90.00  126
 28  \w     30.00 107.00   0.50    6.00    --  111.00 -94.00-120.00  154
 29  \w     53.00 107.00   0.50    6.00    --  111.00 -94.00 -60.00  108
 30  \w     54.00  81.00   0.50    6.00    --  111.00-125.00-180.00   54
 31  \w     39.00  83.00   0.50    6.00    --  111.00-125.00   0.00   88
 32  \w     76.00 101.00   0.50    6.00    --  111.00 -45.00 -60.00   50
 33  \w     60.00  87.00   0.50    6.00    --  111.00 -94.00   0.00   54
 34  \w    113.00 146.00   0.50    6.00    --  111.00  77.00-150.00   66
 35  \w     85.00 133.00   0.50    6.00    --  111.00 -30.00-150.00   96
 36  \w     35.00  60.00   0.50    6.00    --  111.00 -94.00  90.00   50
 37  \w     82.00 107.00   0.50    6.00    --  111.00 -94.00  90.00   50
 38  \w     47.00  76.00   0.50    6.00    --  111.00 -30.00-150.00   58
;
_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      0.0049812000
_diffrn_orient_matrix_UB_12      -0.0810806000
_diffrn_orient_matrix_UB_13      -0.0189158000
_diffrn_orient_matrix_UB_21      -0.0432844000
_diffrn_orient_matrix_UB_22      -0.0160009000
_diffrn_orient_matrix_UB_23      0.0171474000
_diffrn_orient_matrix_UB_31      -0.0149130000
_diffrn_orient_matrix_UB_32      0.0193394000
_diffrn_orient_matrix_UB_33      -0.0651624000
_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  0.0308
_diffrn_reflns_av_unetI/netI     0.0195
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -42
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            164737
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.803
_diffrn_reflns_theta_min         2.641
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.837
_exptl_absorpt_correction_T_max  0.783
_exptl_absorpt_correction_T_min  0.592
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.610
_exptl_crystal_description       block
_exptl_crystal_F_000             6624
_exptl_crystal_size_max          0.218
_exptl_crystal_size_mid          0.139
_exptl_crystal_size_min          0.106
_refine_diff_density_max         0.513
_refine_diff_density_min         -0.558
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2090
_refine_ls_number_reflns         28048
_refine_ls_number_restraints     436
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0381
_refine_ls_R_factor_gt           0.0334
_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^)+(0.0462P)^2^+6.9739P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0859
_refine_ls_wR_factor_ref         0.0894
_reflns_Friedel_coverage         0.000
_reflns_number_gt                25078
_reflns_number_total             28048
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc08693k2.cif
_cod_data_source_block           jjw1379
_cod_depositor_comments
'Adding full bibliography for 1576791--1576804.cif.'
_cod_database_code               1576794
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C38H42F16N4O6P2S2
_reflns_odcompleteness_completeness 99.95
_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
2. Uiso/Uaniso restraints and constraints
S7B \\sim F49B \\sim F50B \\sim F51B \\sim O19B \\sim O20B \\sim O21B \\sim C1B
\\sim S7A \\sim F49A \\sim F50A \\sim F51A \\sim O19A \\sim O20A \\sim O21A
\\sim C115: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(O20B) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(F50A) \\sim Ueq,
Uanis(F49A) \\sim Ueq, Uanis(F51A) \\sim Ueq, Uanis(S7A) \\sim Ueq, Uanis(O21A)
\\sim Ueq, Uanis(O19B) \\sim Ueq, Uanis(O20A) \\sim Ueq, Uanis(C1B) \\sim Ueq,
Uanis(F51B) \\sim Ueq, Uanis(F50B) \\sim Ueq, Uanis(F49B) \\sim Ueq, Uanis(S7B)
\\sim Ueq, Uanis(O21B) \\sim Ueq, Uanis(O19A) \\sim Ueq: with sigma of 0.1 and
sigma for terminal atoms of 0.2
Uanis(C1B) \\sim Ueq, Uanis(O21B) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(O19B) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
3. Rigid body (RIGU) restrains
 S7B, F49B, F50B, F51B, O19B, O20B, O21B, C1B, S7A, F49A, F50A, F51A, O19A,
 O20A, O21A, C115
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O21B, C1B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O19B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(S6B)=Sof(F46B)=Sof(F47B)=Sof(F48B)=Sof(O16B)=Sof(O17B)=Sof(O18B)=Sof(C1A)=
 1-FVAR(1)
 Sof(S6A)=Sof(F46A)=Sof(F47A)=Sof(F48A)=Sof(O16A)=Sof(O17A)=Sof(O18A)=
 Sof(C114)=FVAR(1)
 Fixed Sof: S7B(0.25) F49B(0.25) F50B(0.25) F51B(0.25) O19B(0.25) O20B(0.25)
 O21B(0.25) C1B(0.25) S4(0.5) F40(0.5) F41(0.5) F42(0.5) O10(0.5) O11(0.5)
 O12(0.5) C112(0.5) S7A(0.25) F49A(0.25) F50A(0.25) F51A(0.25) O19A(0.25)
 O20A(0.25) O21A(0.25) C115(0.25)
5.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C11(H11), C17(H17), C22(H22), C37(H37), C38(H38),
 C42(H42), C47(H47), C53(H53), C56(H56), C73(H73), C74(H74), C78(H78), C83(H83),
  C89(H89), C92(H92)
5.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C),
 C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C85(H85A,H85B,
 H85C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C94(H94A,
 H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C)
;
_shelx_res_checksum              39986
_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 1.187
_oxdiff_exptl_absorpt_empirical_full_min 0.885