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_1576734
_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
_chemical_formula_moiety         'C19 H15 F3 O2 S'
_chemical_formula_sum            'C19 H15 F3 O2 S'
_chemical_formula_weight         364.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-16
_audit_creation_method
;
Olex2 1.5-ac6-020
(compiled 2024.02.14 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6966)
;
_audit_update_record
;
2025-07-17 deposited with the CCDC.	2025-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.6591(3)
_cell_length_b                   12.8618(3)
_cell_length_c                   15.7626(4)
_cell_measurement_reflns_used    6984
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.8230
_cell_measurement_theta_min      4.3930
_cell_volume                     1755.51(9)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.981
_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    -54.00 -28.00   0.50    0.29    -- -101.00  57.00-150.00   52
  2  \w    -61.00 -28.00   0.50    0.29    -- -101.00  57.00 -30.00   66
  3  \w    -61.00 -35.00   0.50    0.29    -- -101.00  57.00   0.00   52
  4  \w    -62.00 -28.00   0.50    0.29    -- -101.00  57.00  30.00   68
  5  \w    -11.00  26.00   0.50    0.07    --  -47.95  19.00 120.00   74
  6  \w    -12.00  25.00   0.50    0.07    --  -47.95  57.00 150.00   74
  7  \w    -63.00 -15.00   0.50    0.07    --  -47.95  57.00 150.00   96
  8  \w    -14.00  23.00   0.50    0.07    --  -47.95  19.00 150.00   74
  9  \w    -27.00  19.00   0.50    0.07    --  -47.95  37.00  60.00   92
 10  \w    -28.00  25.00   0.50    0.07    --  -47.95  37.00  30.00  106
 11  \w    -35.00  18.00   0.50    0.07    --  -47.95  37.00 -90.00  106
 12  \w     -8.00  18.00   0.50    0.07    --  -47.95  19.00-180.00   52
 13  \w    118.00 143.00   0.50    0.29    --  107.11   0.00-180.00   50
 14  \w     95.00 167.00   0.50    0.29    --  107.11  19.00 -60.00  144
 15  \w     80.00 154.00   0.50    0.29    --  107.11 125.00   0.00  148
 16  \w     40.00  70.00   0.50    0.29    --  107.11 -57.00 150.00   60
 17  \w     21.00  90.00   0.50    0.07    --   47.95-125.00 -30.00  138
 18  \w     39.00  64.00   0.50    0.29    --  107.11 -57.00 -60.00   50
 19  \w     51.00 102.00   0.50    0.29    --  107.11-125.00 -60.00  102
 20  \w     77.00 106.00   0.50    0.29    --  107.11 -99.00-180.00   58
 21  \w     45.00 105.00   0.50    0.29    --  107.11 -99.00 -60.00  120
 22  \w     38.00  66.00   0.50    0.29    --  107.11 -99.00-180.00   56
 23  \w     71.00  96.00   0.50    0.29    --  107.11 -99.00-120.00   50
 24  \w     43.00 111.00   0.50    0.29    --  107.11-125.00  90.00  136
 25  \w     42.00 106.00   0.50    0.29    --  107.11 -99.00  90.00  128
 26  \w     73.00 103.00   0.50    0.29    --  107.11 -99.00 150.00   60
 27  \w   -112.00 -32.00   0.50    0.29    -- -101.00 125.00 -30.00  160
 28  \w    -81.00 -45.00   0.50    0.29    -- -101.00 125.00  90.00   72
 29  \w   -173.00-101.00   0.50    0.29    -- -101.00 -37.00-150.00  144
 30  \w   -156.00-112.00   0.50    0.29    -- -101.00 -57.00   0.00   88
;
_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      0.0571394000
_diffrn_orient_matrix_UB_12      0.0905438000
_diffrn_orient_matrix_UB_13      -0.0556901000
_diffrn_orient_matrix_UB_21      -0.1582301000
_diffrn_orient_matrix_UB_22      0.0040087000
_diffrn_orient_matrix_UB_23      -0.0446584000
_diffrn_orient_matrix_UB_31      -0.0581605000
_diffrn_orient_matrix_UB_32      0.0782468000
_diffrn_orient_matrix_UB_33      0.0667360000
_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  0.0449
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            14888
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.696
_diffrn_reflns_theta_min         4.437
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.003
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89662
_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    1.379
_exptl_crystal_description       block
_exptl_crystal_F_000             752
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.219
_refine_diff_density_min         -0.200
_refine_diff_density_rms         0.032
_refine_ls_abs_structure_details
;
 Flack x determined using 1038 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.034(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3565
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0392
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0540P)^2^+0.2150P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0981
_refine_ls_wR_factor_ref         0.1099
_reflns_Friedel_coverage         0.716
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.942
_reflns_number_gt                2963
_reflns_number_total             3565
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06981e2.cif
_cod_data_source_block           chenzm-wzw-3-81b_auto
_cod_original_cell_volume        1755.50(8)
_cod_database_code               1576734
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOFS
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.825
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B)
2.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C15(H15), C16(H16), C17(H17),
 C18(H18)
;
_shelx_res_checksum              41421
_shelx_hkl_checksum              30330
_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 2.273
_oxdiff_exptl_absorpt_empirical_full_min 0.345