Chiral Lewis base/Lewis acid/Brønsted acid cooperative catalysis enabled regio- and enantioselective electrophilic sulfenylation/semipinacol rearrangement of allenols.
Wei, Zheng-Wei; Cai, Qing-Yun; Yang, Li-Miao; Huo, Yu-Xuan; Li, Ze-Long; Gong, Xue-Qing; Chen, Zhi-Min; Chemical science 17 (2026) 2802–2810; doi:10.1039/d5sc06981e

data_1576733
_publ_section_title
;
 Chiral Lewis base/Lewis acid/Br&#xf8;nsted acid cooperative catalysis
 enabled regio- and enantioselective electrophilic
 sulfenylation/semipinacol rearrangement of allenols.
;
_journal_issue                   5
_journal_name_full               'Chemical science'
_journal_page_first              2802
_journal_page_last               2810
_journal_paper_doi               10.1039/d5sc06981e
_journal_volume                  17
_journal_year                    2026
_chemical_absolute_configuration 'R, S'
_chemical_formula_moiety         'C28 H25 F3 O2 S'
_chemical_formula_sum            'C28 H25 F3 O2 S'
_chemical_formula_weight         482.54
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-05
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-07-10 deposited with the CCDC.	2025-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.4790(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.8702(2)
_cell_length_b                   6.43820(10)
_cell_length_c                   15.7216(2)
_cell_measurement_reflns_used    19427
_cell_measurement_temperature    100.0(8)
_cell_measurement_theta_max      76.7340
_cell_measurement_theta_min      2.8380
_cell_volume                     1181.45(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-020 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-020 (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(8)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.976
_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    -67.00  23.00   0.50    0.07    --  -47.70  69.00-174.00  180
  2  \w    -81.00 -56.00   0.50    0.27    -- -101.00  69.00-174.00   50
  3  \w    -62.00 -28.00   0.50    0.27    -- -101.00  57.00 -60.00   68
  4  \w   -116.00 -75.00   0.50    0.07    --  -47.70   0.00 120.00   82
  5  \w    -80.00 -35.00   0.50    0.07    --  -47.70 -37.00  90.00   90
  6  \w    -85.00 -58.00   0.50    0.07    --  -47.70 -77.00 150.00   54
  7  \w   -115.00 -90.00   0.50    0.07    --  -47.70 -77.00  90.00   50
  8  \w    -53.00 -26.00   0.50    0.07    --  -47.70 -77.00 150.00   54
  9  \w    -59.00 -26.00   0.50    0.07    --  -47.70 -77.00  90.00   66
 10  \w    -75.00 -28.00   0.50    0.07    --  -47.70 -69.00  53.00   94
 11  \w    -63.00 -33.00   0.50    0.07    --  -47.70 -57.00 -90.00   60
 12  \w    -79.00 -33.00   0.50    0.07    --  -47.70 -57.00 -30.00   92
 13  \w    -74.00 -34.00   0.50    0.07    --  -47.70 -57.00-120.00   80
 14  \w   -117.00 -70.00   0.50    0.07    --  -47.70 -77.00-180.00   94
 15  \w    -64.00 -26.00   0.50    0.07    --  -47.70 -77.00-180.00   76
 16  \w    -83.00 -26.00   0.50    0.07    --  -47.70 -77.00-120.00  114
 17  \w    -65.00 -34.00   0.50    0.07    --  -47.70 -48.00  15.04   62
 18  \w   -118.00 -86.00   0.50    0.07    --  -47.70 -37.00  90.00   64
 19  \w   -130.00 -87.00   0.50    0.27    -- -101.00 -55.00 175.44   86
 20  \w   -112.00 -79.00   0.50    0.27    -- -101.00 -77.00 -30.00   66
 21  \w   -104.00 -79.00   0.50    0.27    -- -101.00 -77.00 -60.00   50
 22  \w   -112.00 -78.00   0.50    0.27    -- -101.00 -77.00 -90.00   68
 23  \w   -103.00 -78.00   0.50    0.27    -- -101.00 -77.00-180.00   50
 24  \w   -103.00 -78.00   0.50    0.27    -- -101.00 -77.00-150.00   50
 25  \w   -163.00-125.00   0.50    0.27    -- -101.00 -77.00-180.00   76
 26  \w   -139.00-110.00   0.50    0.27    -- -101.00 -77.00-150.00   58
 27  \w   -161.00-135.00   0.50    0.27    -- -101.00 -77.00 -90.00   52
 28  \w   -105.00 -79.00   0.50    0.27    -- -101.00 -77.00  16.52   52
 29  \w   -103.00 -78.00   0.50    0.27    -- -101.00 -77.00  90.00   50
 30  \w   -107.00 -82.00   0.50    0.27    -- -101.00 -77.00 120.00   50
 31  \w   -105.00 -79.00   0.50    0.27    -- -101.00 -77.00 150.00   52
 32  \w   -168.00-142.00   0.50    0.27    -- -101.00 -77.00 120.00   52
 33  \w   -132.00 -78.00   0.50    0.27    -- -101.00 -76.00  79.40  108
 34  \w   -107.00 -79.00   0.50    0.27    -- -101.00 -74.00 179.92   56
 35  \w   -171.00 -79.00   0.50    0.27    -- -101.00 -75.00  41.42  184
 36  \w   -144.00 -78.00   0.50    0.27    -- -101.00 -77.00   0.00  132
 37  \w   -163.00 -79.00   0.50    0.27    -- -101.00 -75.00 -21.85  168
 38  \w   -116.00 -81.00   0.50    0.27    -- -101.00 -73.00 -13.59   70
 39  \w   -170.00-126.00   0.50    0.27    -- -101.00 -73.00 -51.28   88
 40  \w   -154.00-124.00   0.50    0.27    -- -101.00 -73.00 -13.59   60
 41  \w   -105.00 -80.00   0.50    0.27    -- -101.00 -73.00 -51.28   50
 42  \w   -105.00 -79.00   0.50    0.27    -- -101.00 -74.00-108.61   52
 43  \w   -109.00 -84.00   0.50    0.27    -- -101.00 -66.00-125.32   50
 44  \w   -109.00 -84.00   0.50    0.27    -- -101.00 -63.00 -87.83   50
 45  \w   -172.00 -84.00   0.50    0.27    -- -101.00 -64.00-146.08  176
 46  \w   -106.00 -81.00   0.50    0.27    -- -101.00 -69.00  53.00   50
 47  \w   -172.00 -88.00   0.50    0.27    -- -101.00 -61.00  56.59  168
 48  \w   -172.00 -85.00   0.50    0.27    -- -101.00 -62.00 140.99  174
 49  \w   -118.00 -85.00   0.50    0.27    -- -101.00 -61.00 148.78   66
 50  \w   -137.00 -86.00   0.50    0.27    -- -101.00 -58.00 111.36  102
 51  \w   -106.00 -81.00   0.50    0.27    -- -101.00 -71.00 117.02   50
 52  \w   -115.00 -86.00   0.50    0.27    -- -101.00 -57.00  90.00   58
 53  \w   -145.00 -87.00   0.50    0.27    -- -101.00 -57.00 120.00  116
 54  \w   -167.00-141.00   0.50    0.27    -- -101.00 -58.00 111.36   52
 55  \w   -166.00 -88.00   0.50    0.27    -- -101.00 -56.00  81.38  156
 56  \w   -164.00-138.00   0.50    0.27    -- -101.00 -55.00 175.44   52
 57  \w   -117.00 -86.00   0.50    0.27    -- -101.00 -57.00   7.77   62
 58  \w   -169.00 -87.00   0.50    0.27    -- -101.00 -57.00 -60.00  164
 59  \w   -171.00 -87.00   0.50    0.27    -- -101.00 -57.00 -90.00  168
 60  \w     37.00  64.00   0.50    0.07    --   47.70  37.00-180.00   54
 61  \w     29.00  67.00   0.50    0.07    --   47.70  69.00-174.00   76
 62  \w     25.00  55.00   0.50    0.07    --   47.70  77.00 -60.00   60
 63  \w     73.00  99.00   0.50    0.07    --   47.70  69.00-174.00   52
 64  \w     25.00  61.00   0.50    0.07    --   47.70  77.00   0.00   72
 65  \w     27.00  69.00   0.50    0.07    --   47.70  77.00  30.00   84
 66  \w     95.00 120.00   0.50    0.07    --   47.70  77.00  30.00   50
 67  \w     85.00 111.00   0.50    0.27    --  107.11  77.00   0.00   52
 68  \w    133.00 167.00   0.50    0.27    --  107.11  69.00-174.00   68
 69  \w     37.00  70.00   0.50    0.27    --  107.11 -57.00 -60.00   66
 70  \w     47.00  72.00   0.50    0.27    --  107.11 -69.00  53.00   50
 71  \w     -9.00  21.00   0.50    0.07    --   47.70 -19.00 120.00   60
 72  \w    -16.00  20.00   0.50    0.07    --   47.70 -69.00  53.00   72
 73  \w     30.00  63.00   0.50    0.07    --   47.70 -69.00  53.00   66
 74  \w     19.00  91.00   0.50    0.07    --   47.70-125.00  60.00  144
 75  \w     45.00  99.00   0.50    0.27    --  107.11 -99.00   0.00  108
 76  \w     40.00  97.00   0.50    0.27    --  107.11 -99.00  30.00  114
 77  \w     47.00 106.00   0.50    0.27    --  107.11 -99.00  60.00  118
 78  \w     39.00  85.00   0.50    0.27    --  107.11 -99.00 -30.00   92
 79  \w     38.00 102.00   0.50    0.27    --  107.11 -99.00-120.00  128
 80  \w     39.00 106.00   0.50    0.27    --  107.11 -99.00-180.00  134
 81  \w     66.00 110.00   0.50    0.27    --  107.11-125.00-120.00   88
 82  \w     38.00 105.00   0.50    0.27    --  107.11 -99.00 -90.00  134
 83  \w     42.00 106.00   0.50    0.27    --  107.11 -99.00 120.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1129344000
_diffrn_orient_matrix_UB_12      -0.1122658000
_diffrn_orient_matrix_UB_13      0.0373484000
_diffrn_orient_matrix_UB_21      0.0583616000
_diffrn_orient_matrix_UB_22      0.1038576000
_diffrn_orient_matrix_UB_23      -0.0688610000
_diffrn_orient_matrix_UB_31      0.0357676000
_diffrn_orient_matrix_UB_32      0.1839010000
_diffrn_orient_matrix_UB_33      0.0615921000
_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  0.0386
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            28860
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.961
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.002
_diffrn_reflns_theta_min         2.858
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.626
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85694
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.141a (Rigaku Oxford Diffraction, 2024)
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    1.356
_exptl_crystal_description       needle
_exptl_crystal_F_000             504
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.140
_refine_diff_density_min         -0.191
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 2005 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.026(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     307
_refine_ls_number_reflns         4783
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0340
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0533P)^2^+0.2009P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0811
_refine_ls_wR_factor_ref         0.0821
_reflns_Friedel_coverage         0.805
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                4636
_reflns_number_total             4783
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06981e2.cif
_cod_data_source_block           chenzmwzw-3-43a_auto
_cod_database_code               1576733
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOS
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
2.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B)
;
_shelx_res_checksum              3525
_shelx_hkl_checksum              81619
_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 1.222
_oxdiff_exptl_absorpt_empirical_full_min 0.725