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_1576735
_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         'C20 H16 Br F3 O S'
_chemical_formula_sum            'C20 H16 Br F3 O S'
_chemical_formula_weight         441.30
_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             2025-06-05
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.01707(12)
_cell_length_b                   9.66742(17)
_cell_length_c                   27.4191(5)
_cell_measurement_reflns_used    14903
_cell_measurement_temperature    99.8(9)
_cell_measurement_theta_max      76.7380
_cell_measurement_theta_min      3.1790
_cell_volume                     1860.03(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.141a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.141a 64-bit (release 04-10-2024))'
_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_environment      N~2~
_diffrn_ambient_temperature      99.8(9)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.978
_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   -167.00-125.00   0.50    0.05    -- -101.00-117.00 -41.00   84
  2  \w   -121.00 -80.00   0.50    0.05    -- -101.00-117.00 -41.00   82
  3  \w   -173.00-103.00   0.50    0.05    -- -101.00 -22.00 160.00  140
  4  \w    -90.00 -41.00   0.50    0.05    -- -101.00 106.00 143.00   98
  5  \w    -63.00 -30.00   0.50    0.05    -- -101.00  57.00   0.00   66
  6  \w    -36.00 -10.00   0.50    0.05    --  -47.95  37.00  60.00   52
  7  \w     -4.00  21.00   0.50    0.05    --  -47.95  19.00  60.00   50
  8  \w      2.00  27.00   0.50    0.05    --  -47.95  19.00 150.00   50
  9  \w   -120.00 -72.00   0.50    0.05    --  -47.95   0.00-120.00   96
 10  \w     81.00 106.00   0.50    0.05    --  107.11-106.00  44.00   50
 11  \w     44.00  70.00   0.50    0.05    --  107.11 -57.00  90.00   52
 12  \w    -15.00  23.00   0.50    0.05    --   47.95 -22.00 160.00   76
 13  \w     41.00  66.00   0.50    0.05    --  107.11 -57.00 -90.00   50
 14  \w    151.00 177.00   0.50    0.05    --  107.11   0.00-120.00   52
 15  \w   -119.00 -87.00   0.50    0.08    --  -47.95   0.00-150.00   64
 16  \w   -100.00 -72.00   0.50    0.08    --  -47.95   0.00 -60.00   56
 17  \w    -11.00  17.00   0.50    0.08    --  -47.95  19.00-180.00   56
 18  \w    -69.00 -30.00   0.50    0.08    --  -47.95  77.00  90.00   78
 19  \w     -6.00  22.00   0.50    0.08    --  -47.95  19.00 -30.00   56
 20  \w     -2.00  28.00   0.50    0.08    --  -47.95  19.00  30.00   60
 21  \w     -6.00  20.00   0.50    0.08    --  -47.95  77.00  90.00   52
 22  \w     20.00  85.00   0.50    0.08    --   47.95-125.00-120.00  130
 23  \w    -63.00 -33.00   0.50    0.22    -- -101.00 125.00  30.00   60
 24  \w    -56.00 -28.00   0.50    0.22    -- -101.00  57.00 150.00   56
 25  \w   -163.00 -92.00   0.50    0.22    -- -101.00 -57.00-120.00  142
 26  \w   -111.00 -86.00   0.50    0.22    -- -101.00 125.00  30.00   50
 27  \w   -108.00 -73.00   0.50    0.22    -- -101.00 109.00 -17.36   70
 28  \w    -66.00 -40.00   0.50    0.22    -- -101.00 109.00 -17.36   52
 29  \w     37.00  62.00   0.50    0.22    --  107.11 -57.00 150.00   50
 30  \w     39.00  65.00   0.50    0.22    --  107.11-125.00-150.00   52
 31  \w     80.00 106.00   0.50    0.22    --  107.11 -99.00 120.00   52
 32  \w     37.00  67.00   0.50    0.22    --  107.11 -99.00  60.00   60
 33  \w     48.00 106.00   0.50    0.22    --  107.11 -99.00-150.00  116
 34  \w    101.00 174.00   0.50    0.22    --  107.11  77.00   0.00  146
 35  \w     35.00  60.00   0.50    0.22    --  107.11 -57.00  30.00   50
 36  \w     41.00  66.00   0.50    0.22    --  107.11 -57.00 -60.00   50
 37  \w     35.00  70.00   0.50    0.22    --  107.11 -57.00 -30.00   70
 38  \w     50.00  76.00   0.50    0.22    --  107.11 -99.00 120.00   52
 39  \w     67.00  98.00   0.50    0.22    --  107.11 -99.00 -90.00   62
 40  \w    135.00 176.00   0.50    0.22    --  107.11 125.00  60.00   82
 41  \w     37.00  63.00   0.50    0.22    --  107.11 -99.00 -90.00   52
 42  \w     78.00 103.00   0.50    0.22    --  107.11-125.00-150.00   50
 43  \w     82.00 108.00   0.50    0.22    --  107.11 125.00  60.00   52
 44  \w    116.00 170.00   0.50    0.22    --  107.11   0.00 -60.00  108
 45  \w     44.00  70.00   0.50    0.22    --  107.11 -57.00-120.00   52
;
_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      0.0283947000
_diffrn_orient_matrix_UB_12      0.1577210000
_diffrn_orient_matrix_UB_13      -0.0036810000
_diffrn_orient_matrix_UB_21      0.0559378000
_diffrn_orient_matrix_UB_22      0.0050178000
_diffrn_orient_matrix_UB_23      0.0543246000
_diffrn_orient_matrix_UB_31      0.2103520000
_diffrn_orient_matrix_UB_32      -0.0223988000
_diffrn_orient_matrix_UB_33      -0.0138667000
_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  0.0388
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            20324
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.132
_diffrn_reflns_theta_min         3.224
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.382
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73190
_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    1.576
_exptl_crystal_description       needle
_exptl_crystal_F_000             888
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.313
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 1470 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.020(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         3795
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0249
_refine_ls_R_factor_gt           0.0231
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0153P)^2^+1.0463P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0520
_refine_ls_wR_factor_ref         0.0532
_reflns_Friedel_coverage         0.701
_reflns_Friedel_fraction_full    0.993
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                3678
_reflns_number_total             3795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06981e2.cif
_cod_data_source_block           chenzmwzw-3-23a_auto
_cod_database_code               1576735
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHOSBr
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.668
_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:
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C13(H13), C16(H16), C17(H17), C18(H18), C19(H19)
2.c X=CH2 refined with riding coordinates:
 C2(H2A,H2B)
;
_shelx_res_checksum              89995
_shelx_hkl_checksum              32583
_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 1.398
_oxdiff_exptl_absorpt_empirical_full_min 0.685