Enantioselective Construction of Chiral Sulfides via Catalytic Electrophilic Azidothiolation and Oxythiolation of N-Allyl Sulfonamides
Liang, Yaoyu; Zhao, Xiaodan; ACS Catalysis 9 (2019) 6896–; doi:10.1021/acscatal.9b01900

data_4514662
_publ_section_title
;
 Enantioselective Construction of Chiral Sulfides via Catalytic
 Electrophilic Azidothiolation and Oxythiolation of N-Allyl Sulfonamides
;
_journal_issue                   8
_journal_name_full               'ACS Catalysis'
_journal_page_first              6896
_journal_paper_doi               10.1021/acscatal.9b01900
_journal_volume                  9
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C24 H24 N2 O2 S3, 0.5(C H Cl3)'
_chemical_formula_sum            'C24.5 H0.5 Cl1.5 N2 O2 S3'
_chemical_formula_weight         504.12
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_space_group_name_Hall  'P 1'
_symmetry_space_group_name_H-M   'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-16
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.07.04 svn.r3439 for OlexSys, GUI svn.r5361)
;
_cell_angle_alpha                72.8010(10)
_cell_angle_beta                 87.8770(10)
_cell_angle_gamma                87.3440(10)
_cell_formula_units_Z            2
_cell_length_a                   5.70840(10)
_cell_length_b                   14.6112(2)
_cell_length_c                   15.7856(2)
_cell_measurement_reflns_used    26865
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.7490
_cell_measurement_theta_min      4.8900
_cell_volume                     1256.02(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5826
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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   -115.00 -11.00   1.00    1.00    --  -40.84 -57.00 150.00  104
  2  \w   -122.00   5.00   1.00    1.00    --  -40.84 -19.00  60.00  127
  3  \w    -70.00  33.00   1.00    1.00    --  -40.84  57.00 150.00  103
  4  \w   -115.00 -11.00   1.00    1.00    --  -40.84 -57.00   0.00  104
  5  \w     23.00  98.00   1.00    1.00    --   40.84-125.00   0.00   75
  6  \w      1.00  83.00   1.00    1.00    --   40.84 -99.00-150.00   82
  7  \w      7.00  33.00   1.00    1.00    --   44.00  88.00-121.92   26
  8  \w     13.00  46.00   1.00    1.00    --   48.00  81.00 150.82   33
  9  \w     13.00  40.00   1.00    1.00    --   48.00  83.00  27.57   27
 10  \w     17.00  45.00   1.00    1.00    --   52.00  82.00 -36.86   28
 11  \w     17.00  46.00   1.00    1.00    --   52.00  81.00 171.19   29
 12  \w     22.00  49.00   1.00    1.00    --   56.00  78.00-105.38   27
 13  \w     22.00  49.00   1.00    1.00    --   56.00  78.00 110.90   27
 14  \w     22.00 135.00   1.00    1.00    --   56.00  77.00  79.75  113
 15  \w     27.00 138.00   1.00    1.00    --   60.00  76.00 179.49  111
 16  \w     26.00 139.00   1.00    1.00    --   60.00  77.00   5.71  113
 17  \w     27.00 138.00   1.00    1.00    --   60.00  76.00 -57.91  111
 18  \w     31.00 142.00   1.00    1.00    --   64.00  75.00 -78.28  111
 19  \w     31.00 142.00   1.00    1.00    --   64.00  76.00-148.11  111
 20  \w     66.00 178.00   1.00    1.02    --  100.00  77.00 -66.93  112
 21  \w     24.00 109.00   1.00    1.02    --  108.22 -94.00-120.00   85
 22  \w     78.00 178.00   1.00    1.02    --  108.22  61.00  30.00  100
 23  \w     75.00 178.00   1.00    1.02    --  108.22  77.00-180.00  103
 24  \w     78.00 178.00   1.00    1.02    --  108.22  61.00 120.00  100
 25  \w     78.00 178.00   1.00    1.02    --  108.22  61.00  90.00  100
 26  \w     75.00 178.00   1.00    1.02    --  108.22  77.00-150.00  103
 27  \w     75.00 178.00   1.00    1.02    --  108.22  77.00   0.00  103
 28  \w     24.00 109.00   1.00    1.02    --  108.22 -94.00-180.00   85
 29  \w     78.00 178.00   1.00    1.02    --  108.22  61.00-180.00  100
 30  \w     78.00 178.00   1.00    1.02    --  108.22  61.00  60.00  100
 31  \w     75.00 178.00   1.00    1.02    --  108.22  77.00  30.00  103
 32  \w     75.00 178.00   1.00    1.02    --  108.22  77.00 150.00  103
 33  \w     78.00 178.00   1.00    1.02    --  108.22  61.00-150.00  100
 34  \w     78.00 178.00   1.00    1.02    --  108.22  61.00 -30.00  100
 35  \w     75.00 178.00   1.00    1.02    --  108.22  77.00-120.00  103
 36  \w     75.00 178.00   1.00    1.02    --  108.22  77.00  60.00  103
 37  \w     78.00 178.00   1.00    1.02    --  108.22  61.00 -90.00  100
 38  \w     75.00 178.00   1.00    1.02    --  108.22  77.00 -30.00  103
 39  \w     75.00 178.00   1.00    1.02    --  108.22  77.00 120.00  103
 40  \w     75.00 178.00   1.00    1.02    --  108.22  77.00  90.00  103
 41  \w     78.00 178.00   1.00    1.02    --  108.22  61.00-120.00  100
 42  \w     94.00 178.00   1.00    1.02    --  108.22 125.00-120.00   84
 43  \w     78.00 178.00   1.00    1.02    --  108.22  61.00 150.00  100
 44  \w     78.00 178.00   1.00    1.02    --  108.22  61.00   0.00  100
 45  \w     30.00 142.00   1.00    1.02    --  108.22 -77.00 -60.00  112
 46  \w     24.00 109.00   1.00    1.02    --  108.22 -94.00  30.00   85
 47  \w     11.00 115.00   1.00    1.00    --   40.84  57.00-150.00  104
 48  \w    -49.00 130.00   1.00    1.00    --   40.84   0.00-150.00  179
 49  \w     15.00 117.00   1.00    1.00    --   40.84  37.00-180.00  102
 50  \w    -49.00 130.00   1.00    1.00    --   40.84   0.00-180.00  179
 51  \w      7.00  33.00   1.00    1.00    --   44.00  88.00 -21.69   26
 52  \w     12.00  38.00   1.00    1.00    --   48.00  84.00 -18.61   26
 53  \w     17.00  46.00   1.00    1.00    --   52.00  81.00 -99.44   29
 54  \w     22.00  49.00   1.00    1.00    --   56.00  78.00-144.78   27
 55  \w     23.00 134.00   1.00    1.00    --   56.00  76.00 -35.91  111
 56  \w     22.00  49.00   1.00    1.00    --   56.00  78.00  23.20   27
 57  \w     22.00  49.00   1.00    1.00    --   56.00  78.00  -2.55   27
 58  \w     22.00 135.00   1.00    1.00    --   56.00  77.00 -66.23  113
 59  \w     29.00 134.00   1.00    1.00    --   60.00  62.00 179.49  105
 60  \w     30.00 143.00   1.00    1.00    --   64.00  77.00-101.69  113
 61  \w     31.00 142.00   1.00    1.00    --   64.00  76.00-139.72  111
 62  \w     81.00 178.00   1.00    1.02    --  108.22  45.00-180.00   97
 63  \w     94.00 178.00   1.00    1.02    --  108.22 125.00  30.00   84
 64  \w     81.00 178.00   1.00    1.02    --  108.22  45.00 120.00   97
 65  \w     75.00 178.00   1.00    1.02    --  108.22  77.00 -60.00  103
 66  \w     75.00 178.00   1.00    1.02    --  108.22  77.00 -90.00  103
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0219185000
_diffrn_orient_matrix_UB_12      0.0379388000
_diffrn_orient_matrix_UB_13      0.0805183000
_diffrn_orient_matrix_UB_21      0.0405659000
_diffrn_orient_matrix_UB_22      -0.1033818000
_diffrn_orient_matrix_UB_23      0.0601987000
_diffrn_orient_matrix_UB_31      0.2662845000
_diffrn_orient_matrix_UB_32      0.0084706000
_diffrn_orient_matrix_UB_33      -0.0183348000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0317
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            43701
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.931
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.850
_diffrn_reflns_theta_min         3.628
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.367
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.20403
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.333
_exptl_crystal_description       needle
_exptl_crystal_F_000             502
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.095
_refine_diff_density_min         -0.840
_refine_diff_density_rms         0.089
_refine_ls_abs_structure_details
;
 Flack x determined using 4114 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.002(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     597
_refine_ls_number_reflns         9469
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0576
_refine_ls_R_factor_gt           0.0548
_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^)+(0.1010P)^2^+1.3388P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1520
_refine_ls_wR_factor_ref         0.1558
_reflns_Friedel_coverage         0.886
_reflns_Friedel_fraction_full    0.905
_reflns_Friedel_fraction_max     0.874
_reflns_number_gt                9157
_reflns_number_total             9469
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01900_si_002.cif
_cod_data_source_block           17082903
_cod_original_formula_sum        'C24.50 H0.50 Cl1.50 N2 O2 S3'
_cod_database_code               4514662
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C H N S'
_chemical_oxdiff_usercomment     1489
_reflns_odcompleteness_completeness 99.96
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C10(H10), C35(H35), C34(H34), C01T(H01T)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C33(H33A,H33B), C18(H18A,H18B), C42(H42A,H42B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N3(H3A), C30(H30), C28(H28), C41(H41), C13(H13), C40(H40), C4(H4),
 C27(H27), C6(H6), C15(H15), C31(H31), C7(H7), C14(H14), C37(H37), C3(H3),
 C39(H39), C17(H17), C16(H16), C20(H20), C48(H48), C46(H46), C47(H47), C24(H24),
  C38(H38), C44(H44), C45(H45), C21(H21), C22(H22), C23(H23)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C25(H25A,H25B,H25C)
;
_shelx_res_checksum              62943
_shelx_hkl_checksum              8780
_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 2.447
_oxdiff_exptl_absorpt_empirical_full_min 0.508