Chiral Brønsted acid-catalyzed asymmetric dearomative spirocyclization of alkynyl thioethers
Fan, Xin-Yang; Li, Jia-Cheng; Zhou, Ji-Jia; Zhou, Bo; Ye, Long-Wu; Green Chemistry 25 (2023) 10638–10643; doi:10.1039/D3GC03222A

data_7247742
_publ_section_title
;
 Chiral Br\/onsted acid-catalyzed asymmetric dearomative spirocyclization
 of alkynyl thioethers
;
_journal_issue                   24
_journal_name_full               'Green Chemistry'
_journal_page_first              10638
_journal_page_last               10643
_journal_paper_doi               10.1039/D3GC03222A
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C24 H23 Br O S'
_chemical_formula_sum            'C24 H23 Br O S'
_chemical_formula_weight         439.39
_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             2023-07-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-08-18 deposited with the CCDC.	2023-11-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.82940(10)
_cell_length_b                   14.2435(2)
_cell_length_c                   20.7154(2)
_cell_measurement_reflns_used    10178
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.4340
_cell_measurement_theta_min      3.7530
_cell_volume                     2015.08(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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    -83.00 -56.00   1.00    1.00    --  -40.50 125.00 -30.00   27
  2  \w   -108.00 -18.00   1.00    1.00    --  -40.50 -57.00 120.00   90
  3  \w    -64.00  30.00   1.00    1.00    --  -40.50  57.00 -90.00   94
  4  \w    -61.00  32.00   1.00    1.00    --  -40.50  37.00  60.00   93
  5  \w     17.00  53.00   1.00    1.00    --   43.04 -99.00  60.00   36
  6  \w     99.00 178.00   1.00    1.20    --  107.03  30.00 120.00   79
  7  \w     39.00 133.00   1.00    1.20    --  107.03 -77.00  30.00   94
  8  \w     52.00 130.00   1.00    1.20    --  107.03 -45.00  60.00   78
  9  \w    111.00 177.00   1.00    1.20    --  107.03  77.00 150.00   66
 10  \w    109.00 175.00   1.00    1.20    --  107.03  77.00-150.00   66
 11  \w     62.00 110.00   1.00    1.20    --  107.03-125.00-120.00   48
 12  \w    127.00 153.00   1.00    1.20    --  107.03  77.00-180.00   26
 13  \w     68.00 107.00   1.00    1.20    --  107.03 -94.00-150.00   39
 14  \w     32.00 127.00   1.00    1.20    --  107.03 -30.00 150.00   95
 15  \w    100.00 127.00   1.00    1.20    --  107.03 -45.00-180.00   27
 16  \w     53.00 107.00   1.00    1.20    --  107.03 -94.00 -90.00   54
 17  \w     32.00 108.00   1.00    1.20    --  107.03-102.00   0.56   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0242060000
_diffrn_orient_matrix_UB_12      -0.0807689000
_diffrn_orient_matrix_UB_13      0.0488649000
_diffrn_orient_matrix_UB_21      0.0337922000
_diffrn_orient_matrix_UB_22      0.0693186000
_diffrn_orient_matrix_UB_23      0.0559607000
_diffrn_orient_matrix_UB_31      -0.2217048000
_diffrn_orient_matrix_UB_32      0.0192946000
_diffrn_orient_matrix_UB_33      0.0032398000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0364
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            14232
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.402
_diffrn_reflns_theta_min         3.766
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.821
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45645
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic light white'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       plate
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.01
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.526
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1604 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.000(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         4078
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0275
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0370P)^2^+0.4300P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0648
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.723
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                3892
_reflns_number_total             4078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc03222a2.cif
_cod_data_source_block           exp_19291_auto
_cod_depositor_comments          'Adding full bibliography for 7247742.cif.'
_cod_database_code               7247742
_shelxl_version_number           2013-2
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C2(H2), C4(H4), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C20(H20), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              47785
_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 2.002
_oxdiff_exptl_absorpt_empirical_full_min 0.629