Catalytic enantioselective alkenylation-heteroarylation of olefins: stereoselective syntheses of 5-7 membered azacycles and oxacycles.
Ma, Zhaoming; Sun, Lantian; Zhou, Jianrong Steve; Chemical science 14 (2023) 3010–3017; doi:10.1039/d2sc07117g

data_1568405
_publ_section_title
;
 Catalytic enantioselective alkenylation-heteroarylation of olefins:
 stereoselective syntheses of 5-7 membered azacycles and oxacycles.
;
_journal_issue                   11
_journal_name_full               'Chemical science'
_journal_page_first              3010
_journal_page_last               3017
_journal_paper_doi               10.1039/d2sc07117g
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H18 N2 O3 S2'
_chemical_formula_sum            'C18 H18 N2 O3 S2'
_chemical_formula_weight         374.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-02-17 deposited with the CCDC.	2023-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.4012(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   10.53468(11)
_cell_length_b                   6.40021(7)
_cell_length_c                   13.58053(14)
_cell_measurement_reflns_used    11070
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      77.3680
_cell_measurement_theta_min      3.3690
_cell_volume                     878.396(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.963
_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     41.00  87.00   0.50    0.05    --   48.98  38.00  79.00   92
  2  \w     83.00 117.00   0.50    0.05    --   48.98  77.00 150.00   68
  3  \w     29.00  76.00   0.50    0.05    --   48.98  77.00 150.00   94
  4  \w     37.00 100.00   0.50    0.05    --   48.98  57.00-120.00  126
  5  \w    -13.00  12.00   0.50    0.05    --   48.98 -38.00 -75.00   50
  6  \w     34.00  68.00   0.50    0.06    --  105.71 -57.00-180.00   68
  7  \w     39.00 105.00   0.50    0.06    --  105.71 -77.00 -30.00  132
  8  \w     82.00 108.00   0.50    0.06    --  105.71 -77.00  90.00   52
  9  \w     34.00  60.00   0.50    0.06    --  105.71 -57.00 150.00   52
 10  \w     38.00  75.00   0.50    0.06    --  105.71 -77.00  90.00   74
 11  \w     98.00 178.00   0.50    0.06    --  105.71  19.00 -60.00  160
 12  \w    111.00 144.00   0.50    0.06    --  105.71  38.00  79.00   66
 13  \w     86.00 111.00   0.50    0.06    --  105.71  77.00 150.00   50
 14  \w    -22.00   6.00   0.50    0.05    --  -48.98  19.00  30.00   56
 15  \w    -29.00  -2.00   0.50    0.05    --  -48.98  38.00  79.00   54
 16  \w    -24.00  25.00   0.50    0.05    --  -48.98  19.00  60.00   98
 17  \w     55.00  93.00   0.50    0.06    --  105.71 -99.00   0.00   76
 18  \w    -23.00  23.00   0.50    0.05    --  -48.98  19.00-120.00   92
 19  \w    -92.00 -47.00   0.50    0.06    -- -104.00  77.00 -30.00   90
 20  \w    -64.00 -32.00   0.50    0.06    -- -104.00  57.00  90.00   64
 21  \w    -63.00 -33.00   0.50    0.06    -- -104.00  57.00 -60.00   60
 22  \w    -63.00 -32.00   0.50    0.06    -- -104.00  57.00 -90.00   62
 23  \w    -61.00 -36.00   0.50    0.06    -- -104.00  57.00-180.00   50
 24  \w   -130.00-105.00   0.50    0.06    -- -104.00 -19.00-150.00   50
 25  \w   -109.00 -84.00   0.50    0.06    -- -104.00 -77.00-180.00   50
 26  \w   -109.00 -83.00   0.50    0.06    -- -104.00 -77.00-120.00   52
 27  \w   -108.00 -83.00   0.50    0.06    -- -104.00 -77.00-150.00   50
 28  \w   -175.00 -83.00   0.50    0.06    -- -104.00 -77.00 -90.00  184
 29  \w   -174.00-125.00   0.50    0.06    -- -104.00 -60.00-161.47   98
 30  \w   -116.00 -90.00   0.50    0.06    -- -104.00 -60.00-161.47   52
 31  \w   -169.00 -94.00   0.50    0.06    -- -104.00 -57.00-180.00  150
 32  \w   -156.00 -92.00   0.50    0.06    -- -104.00 -77.00 150.00  128
 33  \w   -114.00 -88.00   0.50    0.06    -- -104.00 -66.00 144.65   52
 34  \w   -117.00 -91.00   0.50    0.06    -- -104.00 -57.00 150.00   52
 35  \w   -124.00 -96.00   0.50    0.06    -- -104.00 -54.00 141.94   56
 36  \w   -115.00 -90.00   0.50    0.06    -- -104.00 -60.00 169.17   50
 37  \w    -77.00 -51.00   0.50    0.05    --  -48.98 -57.00 150.00   52
 38  \w   -158.00-132.00   0.50    0.06    -- -104.00 -38.00 -75.00   52
 39  \w   -110.00 -41.00   0.50    0.05    --  -48.98 -38.00 -75.00  138
 40  \w   -118.00 -93.00   0.50    0.06    -- -104.00 -54.00-132.20   50
 41  \w   -138.00 -95.00   0.50    0.06    -- -104.00 -48.00-147.07   86
 42  \w   -174.00-147.00   0.50    0.06    -- -104.00 -48.00-147.07   54
 43  \w   -154.00-127.00   0.50    0.06    -- -104.00 -82.00-127.04   54
 44  \w   -112.00 -86.00   0.50    0.06    -- -104.00 -90.00-172.31   52
 45  \w   -113.00 -81.00   0.50    0.06    -- -104.00 -82.00-127.04   64
 46  \w   -119.00 -82.00   0.50    0.05    --  -48.98-125.00   0.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1334702000
_diffrn_orient_matrix_UB_12      -0.1161843000
_diffrn_orient_matrix_UB_13      -0.0276561000
_diffrn_orient_matrix_UB_21      0.0038293000
_diffrn_orient_matrix_UB_22      -0.0039116000
_diffrn_orient_matrix_UB_23      0.1142251000
_diffrn_orient_matrix_UB_31      -0.0735564000
_diffrn_orient_matrix_UB_32      0.2107722000
_diffrn_orient_matrix_UB_33      -0.0131752000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0197
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11363
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.626
_diffrn_reflns_theta_min         3.392
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.921
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48744
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_description       block
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.210
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1531 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.008(10)
_refine_ls_extinction_coef       0.009(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3511
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0252
_refine_ls_R_factor_gt           0.0251
_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^)+(0.0497P)^2^+0.1452P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0684
_refine_ls_wR_factor_ref         0.0686
_reflns_Friedel_coverage         0.786
_reflns_Friedel_fraction_full    0.973
_reflns_Friedel_fraction_max     0.913
_reflns_number_gt                3500
_reflns_number_total             3511
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc07117g3.cif
_cod_data_source_block           mzm-1227_auto
_cod_depositor_comments          'Adding full bibliography for 1568405.cif.'
_cod_original_cell_volume        878.396(16)
_cod_database_code               1568405
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H O S N'
_shelx_estimated_absorpt_t_max   0.721
_shelx_estimated_absorpt_t_min   0.621
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S21A-C22 \\sim S21-C22
 with sigma of 0.02
 C25A-C24A \\sim C25-C24
 with sigma of 0.02
 C23-C22 \\sim C23A-C22
 with sigma of 0.02
 S21A-C25A \\sim S21-C25
 with sigma of 0.02
 C24-C23 \\sim C24A-C23A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S21 \\sim C23 \\sim C25 \\sim C24 \\sim C23A \\sim C24A \\sim C25A \\sim S21A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C23A, C25A, S21A, C24A, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 S21, C25, C24, C23, C22
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Others
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=Sof(S21A)=1-FVAR(1)
 Sof(S21)=Sof(C23)=Sof(H23)=Sof(C25)=Sof(H25)=Sof(C24)=Sof(H24)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C14(H14A,H14B)
6.b Aromatic/amide H refined with riding coordinates:
 C23(H23), C6(H6), C7(H7), C4(H4), C5(H5), C25(H25), C24(H24), C23A(H23A),
 C24A(H24A), C25A(H25A)
6.c Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              87567
_shelx_hkl_checksum              1324
_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 1.919
_oxdiff_exptl_absorpt_empirical_full_min 0.655