Enantioselective synthesis of 1,2-disubstituted thiocyclobutanes via Michael addition
Robert, Emma G. L.; Waser, Jerome; Chemical Science 16 (2025) 12115–12121; doi:10.1039/D5SC01727K

data_1574706
_publ_section_title
;
 Enantioselective synthesis of 1,2-disubstituted thiocyclobutanes via
 Michael addition
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              12115
_journal_page_last               12121
_journal_paper_doi               10.1039/D5SC01727K
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C18 H18 O3 S'
_chemical_formula_sum            'C18 H18 O3 S'
_chemical_formula_weight         314.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-09-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-10 deposited with the CCDC.	2025-05-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.5193(14)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.0857(3)
_cell_length_b                   5.32972(8)
_cell_length_c                   31.1946(4)
_cell_measurement_reflns_used    14380
_cell_measurement_temperature    139.98(10)
_cell_measurement_theta_max      74.0400
_cell_measurement_theta_min      2.8050
_cell_volume                     3170.09(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      139.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.985
_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     33.00  70.62   0.38    1.50    --   63.59 -95.00-180.00   99
  2  \w     26.00  51.46   0.38    1.50    --   63.59 -95.00 -30.00   67
  3  \w     28.00  59.16   0.38    1.50    --   63.59 -95.00   0.00   82
  4  \w     27.00  60.06   0.38    1.50    --   63.59 -95.00  30.00   87
  5  \w   -109.00 -44.78   0.38    1.50    --  -64.30 -15.00 120.00  169
  6  \w    -91.00 -35.90   0.38    1.50    --  -64.30 125.00-120.00  145
  7  \w    -66.00 -30.66   0.38    1.50    --  -64.30   0.00 150.00   93
  8  \w    -84.00 -33.84   0.38    1.50    --  -71.11 111.00  30.00  132
  9  \w    -72.00 -45.78   0.38    1.50    --  -71.11   0.00 -30.00   69
 10  \w    -68.20 -34.00   0.38    1.50    --  -71.11   0.00   0.00   90
 11  \w    -72.00 -30.96   0.38    1.50    --  -71.11 111.00  90.00  108
 12  \w    -67.06 -34.00   0.38    1.50    --  -71.11   0.00  60.00   87
 13  \w    -67.00 -33.94   0.38    1.50    --  -71.11   0.00-150.00   87
 14  \w    -89.00 -32.00   0.38    1.50    --  -71.11 111.00-150.00  150
 15  \w    -64.00 -38.92   0.38    1.50    --  -71.11   0.00 120.00   66
 16  \w     40.00  66.22   0.38    1.50    --   75.74-111.00 -90.00   69
 17  \w     56.00  82.22   0.38    1.50    --   75.74-111.00  90.00   69
 18  \w     53.00  79.22   0.38    1.50    --   75.74   0.00  30.00   69
 19  \w     42.00  68.22   0.38    1.50    --   75.74-111.00 -30.00   69
 20  \w     53.00  79.22   0.38    1.50    --   75.74-111.00  30.00   69
 21  \w     50.00  76.22   0.38    1.50    --   75.74 -95.00 -30.00   69
 22  \w     36.00  80.08   0.38    1.50    --   75.74-111.00 120.00  116
 23  \w    -63.00 -35.64   0.38    1.50    --  -76.25 136.00 164.87   72
 24  \w   -111.00 -84.78   0.38    1.50    --  -76.25 -77.00  28.83   69
 25  \w   -104.00 -78.92   0.38    1.50    --  -76.25 126.00  24.73   66
 26  \w    -65.00 -39.92   0.38    1.50    --  -76.25 123.00 173.83   66
 27  \w   -109.00 -81.64   0.38    1.50    --  -76.25 -76.00  64.70   72
 28  \w   -111.00 -83.64   0.38    1.50    --  -76.25 136.00 164.87   72
 29  \w   -110.00 -81.88   0.38    1.50    --  -76.25 -83.00  45.02   74
 30  \w   -106.00 -79.78   0.38    1.50    --  -76.25 129.00 162.36   69
 31  \w    -70.00 -45.68   0.38    1.50    --  -76.25 104.00  59.01   64
 32  \w   -107.00 -78.12   0.38    1.50    --  -76.25 130.00-101.96   76
 33  \w    -64.00 -34.74   0.38    1.50    --  -76.25 126.00  24.73   77
 34  \w   -106.00 -80.92   0.38    1.50    --  -76.25 -76.00-179.89   66
 35  \w     54.00  80.22   0.38    1.50    --   76.43-125.00-120.00   69
 36  \w     40.00  65.08   0.38    1.50    --   76.43 -95.00 150.00   66
 37  \w     39.00  64.08   0.38    1.50    --   76.43 -95.00 120.00   66
 38  \w     49.00  82.82   0.38    1.50    --   76.43 -95.00 -60.00   89
 39  \w     58.00  84.22   0.38    1.50    --   76.43 -95.00-120.00   69
 40  \w     67.00 102.34   0.38    1.50    --   76.43-125.00  90.00   93
 41  \w     60.00  93.82   0.38    1.50    --   76.43-125.00 120.00   89
 42  \w     77.00 102.08   0.38    1.50    --   76.43-125.00   0.00   66
 43  \w     36.00  64.12   0.38    1.50    --   76.43-125.00   0.00   74
 44  \w     45.00  70.08   0.38    1.50    --   76.43 -95.00 -90.00   66
 45  \w     52.00  78.22   0.38    1.50    --   76.43 -95.00  30.00   69
 46  \w     55.00  80.08   0.38    1.50    --   76.43-125.00 150.00   66
 47  \w     75.00 100.08   0.38    1.50    --   76.43-125.00  30.00   66
 48  \w     77.00 102.08   0.38    1.50    --   76.43-125.00 -60.00   66
 49  \w     40.00  68.12   0.38    1.50    --   76.43 -95.00   0.00   74
 50  \w     80.00 122.94   0.38    1.50    --   79.75  13.00 156.22  113
 51  \w     63.00 124.94   0.38    1.50    --   79.75  21.00-103.75  163
 52  \w     45.00  75.78   0.38    1.50    --   79.75 -87.00  38.56   81
 53  \w     91.00 120.64   0.38    1.50    --   79.75  21.00  -7.83   78
 54  \w     39.00 108.16   0.38    1.50    --   79.75-132.00-170.02  182
 55  \w     64.00 106.94   0.38    1.50    --   79.75  22.00  27.01  113
 56  \w     56.00 100.08   0.38    1.50    --   79.75-119.00-145.92  116
 57  \w     56.00 110.72   0.38    1.50    --   79.75   0.00 137.31  144
 58  \w     61.00 124.08   0.38    1.50    --   79.75  21.00 -35.31  166
 59  \w     37.00  62.08   0.38    1.50    --   79.75 -54.00-169.21   66
 60  \w     77.00 123.36   0.38    1.50    --   79.75  19.00  60.14  122
 61  \w     49.00 103.34   0.38    1.50    --   79.75-120.00 151.22  143
 62  \w     65.00 106.80   0.38    1.50    --   79.75  22.00-150.39  110
 63  \w     58.00 107.40   0.38    1.50    --   79.75-126.00  53.59  130
 64  \w     54.00  89.72   0.38    1.50    --   79.75   1.00  93.66   94
 65  \w     51.00  91.28   0.38    1.50    --   79.75   4.00-103.76  106
 66  \w     56.00 103.88   0.38    1.50    --   79.75-125.00 -38.35  126
 67  \w     66.00  94.12   0.38    1.50    --   79.75  23.00 109.99   74
 68  \w     61.00 106.22   0.38    1.50    --   79.75-125.00 -45.47  119
 69  \w     51.00 108.76   0.38    1.50    --   79.75-129.00-148.24  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0109420000
_diffrn_orient_matrix_UB_12      0.2861151000
_diffrn_orient_matrix_UB_13      -0.0017522000
_diffrn_orient_matrix_UB_21      0.0771419000
_diffrn_orient_matrix_UB_22      -0.0345361000
_diffrn_orient_matrix_UB_23      0.0155292000
_diffrn_orient_matrix_UB_31      0.0213696000
_diffrn_orient_matrix_UB_32      -0.0220728000
_diffrn_orient_matrix_UB_33      -0.0469045000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            31855
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.774
_diffrn_reflns_theta_min         2.836
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.896
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.642
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
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            'clear pale colourless'
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       prism
_exptl_crystal_F_000             1328
_exptl_crystal_size_max          0.221
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.303
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     274
_refine_ls_number_reflns         3263
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0438
_refine_ls_R_factor_gt           0.0365
_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^)+(0.0555P)^2^+2.0809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0948
_refine_ls_wR_factor_ref         0.0997
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2815
_reflns_number_total             3263
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01727k2.cif
_cod_data_source_block           egr-07-142
_cod_depositor_comments
'Adding full bibliography for 1574706--1574707.cif.'
_cod_database_code               1574706
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C18 H18 O3 S1'
_shelx_estimated_absorpt_t_max   0.931
_shelx_estimated_absorpt_t_min   0.679
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H,H,H) groups
2. Others
 Sof(H12C)=Sof(H12D)=Sof(C19)=Sof(C24)=Sof(H24)=Sof(C23)=Sof(H23)=Sof(C22)=
 Sof(H22)=Sof(C21)=Sof(H21)=Sof(C20)=Sof(H20)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(H18)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C12(H12C,H12D)
3.b Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C24(H24), C23(H23),
 C22(H22), C21(H21), C20(H20)
3.c Fitted hexagon refined as free rotating group:
 C13(C14,C15,C16,C17,C18), C19(C24,C23,C22,C21,C20)
;
_shelx_res_checksum              82867
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.530
_oxdiff_exptl_absorpt_empirical_full_min 0.627