Enantioselective Construction of Spiro-Tetrahydroquinoline Scaffolds through Asymmetric Catalytic Cascade Reactions
Zhang , Jia-Lu; Ma, Rui; Zhao, Huan-Huan; Xu, Peng-Fei; Chemical Communications  (2022) –; doi:10.1039/D2CC00502F

data_7129714
_publ_section_title
;
 Enantioselective Construction of Spiro-Tetrahydroquinoline Scaffolds
 through Asymmetric Catalytic Cascade Reactions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC00502F
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C38 H31 N O6 S, C H Cl3'
_chemical_formula_sum            'C39 H32 Cl3 N O6 S'
_chemical_formula_weight         749.06
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-01-15
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2018.11.30 svn.r3537 for Rigaku Oxford Diffraction, GUI svn.r5622)
;
_audit_update_record
;
2021-05-20 deposited with the CCDC.	2022-02-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.1800(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.77070(10)
_cell_length_b                   9.87040(10)
_cell_length_c                   19.0616(2)
_cell_measurement_reflns_used    22564
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.7970
_cell_measurement_theta_min      2.3120
_cell_volume                     1819.61(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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     27.00  57.00   0.50    0.05    --   46.32  77.00 -30.00   60
  2  \w     24.00  50.00   0.50    0.05    --   46.32  77.00 -60.00   52
  3  \w     24.00  49.00   0.50    0.05    --   46.32  77.00   0.00   50
  4  \w     32.00  59.00   0.50    0.05    --   46.32  57.00 -60.00   54
  5  \w     25.00  52.00   0.50    0.05    --   46.32  77.00 -90.00   54
  6  \w     24.00  51.00   0.50    0.05    --   46.32  77.00-120.00   54
  7  \w     33.00  65.00   0.50    0.05    --   46.32  57.00-150.00   64
  8  \w     26.00  67.00   0.50    0.05    --   46.32  77.00-180.00   82
  9  \w     39.00  68.00   0.50    0.05    --   46.32  57.00-120.00   58
 10  \w     35.00  94.00   0.50    0.05    --   46.32  19.00 -60.00  118
 11  \w     23.00  48.00   0.50    0.05    --   46.32   3.00-156.00   50
 12  \w    -65.00 -31.00   0.50    0.05    --  -46.32 -67.00 -14.48   68
 13  \w    -81.00 -34.00   0.50    0.05    --  -46.32 -37.00 -30.00   94
 14  \w    -98.00 -55.00   0.50    0.05    --  -46.32  -3.00  24.00   86
 15  \w    -86.00 -36.00   0.50    0.05    --  -46.32 -37.00 -90.00  100
 16  \w    -42.00 -17.00   0.50    0.05    --  -46.32   3.00-156.00   50
 17  \w    -93.00 -14.00   0.50    0.05    --  -46.32 125.00 -30.00  158
 18  \w    -69.00 -29.00   0.50    0.10    -- -102.00  61.00-180.00   80
 19  \w      4.00  29.00   0.50    0.05    --  -46.32  27.00 -67.12   50
 20  \w     88.00 174.00   0.50    0.10    --  103.99  61.00-120.00  172
 21  \w    123.00 155.00   0.50    0.10    --  103.99  -3.00  24.00   64
 22  \w    102.00 127.00   0.50    0.10    --  103.99   3.00-156.00   50
 23  \w     32.00  73.00   0.50    0.10    --  103.99 -61.00-180.00   82
 24  \w     31.00 103.00   0.50    0.10    --  103.99 -94.00-180.00  144
 25  \w     27.00  67.00   0.50    0.05    --   46.32-125.00-150.00   80
 26  \w     32.00 106.00   0.50    0.10    --  103.99 -94.00 -90.00  148
 27  \w     58.00  84.00   0.50    0.10    --  103.99 -94.00 -60.00   52
 28  \w     31.00 112.00   0.50    0.10    --  103.99-125.00  90.00  162
 29  \w     33.00 105.00   0.50    0.10    --  103.99 -94.00 120.00  144
 30  \w   -104.00 -78.00   0.50    0.10    -- -102.00 -80.00 -37.92   52
 31  \w   -107.00 -81.00   0.50    0.10    -- -102.00 -78.00 -10.70   52
 32  \w   -175.00-110.00   0.50    0.10    -- -102.00 -78.00 -10.70  130
 33  \w   -162.00-136.00   0.50    0.10    -- -102.00 -77.00   0.00   52
 34  \w   -105.00 -79.00   0.50    0.10    -- -102.00 -77.00  60.00   52
 35  \w   -104.00 -79.00   0.50    0.10    -- -102.00 -77.00 -30.00   50
 36  \w   -106.00 -79.00   0.50    0.10    -- -102.00 -78.00 -51.65   54
 37  \w   -115.00 -84.00   0.50    0.10    -- -102.00 -77.00 -60.00   62
 38  \w   -104.00 -79.00   0.50    0.10    -- -102.00 -77.00-120.00   50
 39  \w   -106.00 -80.00   0.50    0.10    -- -102.00 -77.00-150.00   52
 40  \w   -172.00-146.00   0.50    0.10    -- -102.00 -77.00-120.00   52
 41  \w   -169.00-144.00   0.50    0.10    -- -102.00 -77.00 -60.00   50
 42  \w   -112.00 -83.00   0.50    0.10    -- -102.00 -77.00 -90.00   58
 43  \w   -106.00 -80.00   0.50    0.10    -- -102.00 -74.00-134.53   52
 44  \w   -105.00 -80.00   0.50    0.10    -- -102.00 -75.00-106.72   50
 45  \w   -106.00 -81.00   0.50    0.10    -- -102.00 -73.00 -87.92   50
 46  \w   -104.00 -79.00   0.50    0.10    -- -102.00 -77.00   0.00   50
 47  \w   -108.00 -82.00   0.50    0.10    -- -102.00 -71.00 -30.07   52
 48  \w   -106.00 -81.00   0.50    0.10    -- -102.00 -72.00  -2.44   50
 49  \w   -105.00 -80.00   0.50    0.10    -- -102.00 -77.00  30.00   50
 50  \w   -117.00 -81.00   0.50    0.10    -- -102.00 -72.00  42.81   72
 51  \w   -125.00 -81.00   0.50    0.10    -- -102.00 -72.00  31.98   88
 52  \w   -108.00 -83.00   0.50    0.10    -- -102.00 -71.00  11.89   50
 53  \w   -110.00 -84.00   0.50    0.10    -- -102.00 -64.00 -22.43   52
 54  \w   -112.00 -85.00   0.50    0.10    -- -102.00 -63.00 -31.15   54
 55  \w   -107.00 -82.00   0.50    0.10    -- -102.00 -69.00 -87.38   50
 56  \w   -110.00 -85.00   0.50    0.10    -- -102.00 -61.00 -90.00   50
 57  \w   -111.00 -86.00   0.50    0.10    -- -102.00 -61.00 -51.65   50
 58  \w   -166.00-141.00   0.50    0.10    -- -102.00 -69.00 -87.38   50
 59  \w   -127.00 -85.00   0.50    0.10    -- -102.00 -61.00 -63.76   84
 60  \w   -110.00 -85.00   0.50    0.10    -- -102.00 -61.00   0.00   50
 61  \w   -123.00 -85.00   0.50    0.10    -- -102.00 -62.00  -6.84   76
 62  \w   -110.00 -85.00   0.50    0.10    -- -102.00 -61.00  60.00   50
 63  \w   -144.00-117.00   0.50    0.10    -- -102.00 -61.00  60.00   54
 64  \w   -160.00-135.00   0.50    0.10    -- -102.00 -62.00  -6.84   50
 65  \w   -144.00 -91.00   0.50    0.10    -- -102.00 -45.00  -9.65  106
 66  \w   -111.00 -86.00   0.50    0.10    -- -102.00 -60.00 -40.69   50
 67  \w   -131.00-106.00   0.50    0.10    -- -102.00 -45.00-101.13   50
 68  \w   -110.00 -85.00   0.50    0.10    -- -102.00 -61.00-120.00   50
 69  \w   -114.00 -89.00   0.50    0.10    -- -102.00 -47.00-143.75   50
 70  \w   -173.00-147.00   0.50    0.10    -- -102.00 -47.00-143.75   52
 71  \w   -114.00 -89.00   0.50    0.10    -- -102.00  -3.00  24.00   50
 72  \w    -85.00 -59.00   0.50    0.10    -- -102.00  -3.00  24.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1079032000
_diffrn_orient_matrix_UB_12      0.0015676000
_diffrn_orient_matrix_UB_13      0.0673498000
_diffrn_orient_matrix_UB_21      0.1171323000
_diffrn_orient_matrix_UB_22      -0.0072837000
_diffrn_orient_matrix_UB_23      -0.0460950000
_diffrn_orient_matrix_UB_31      0.0044030000
_diffrn_orient_matrix_UB_32      0.1558585000
_diffrn_orient_matrix_UB_33      -0.0028617000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_unetI/netI     0.0268
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            31466
_diffrn_reflns_point_group_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.023
_diffrn_reflns_theta_min         2.342
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.211
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64330
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             776
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.043
_refine_ls_abs_structure_details
;
 Flack x determined using 2533 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.003(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         6907
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0582P)^2^+0.2230P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1057
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    0.887
_reflns_Friedel_fraction_max     0.834
_reflns_number_gt                6395
_reflns_number_total             6907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc00502f2.cif
_cod_data_source_block           zhangjialu_0112
_cod_database_code               7129714
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.856
_shelx_estimated_absorpt_t_min   0.699
_diffrn_oxdiff_digest_frames
;
0190aa058f6d47442bc6a75233f6f4f46400060c7c5
;
_diffrn_oxdiff_digest_hkl
;
01e9c3ac1e364ae659a2072b729e370af5f881
;
_reflns_odcompleteness_completeness 99.86
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C24) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9), C48(H48)
3.b Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B)
3.c Aromatic/amide H refined with riding coordinates:
 C41(H41), C13(H13), C37(H37), C2(H2), C3(H3), C5(H5), C14(H14), C45(H45),
 C4(H4), C36(H36), C16(H16), C35(H35), C15(H15), C34(H34), C44(H44), C42(H42),
 C21(H21), C24(H24), C23(H23), C25(H25), C22(H22)
3.d Idealised Me refined as rotating group:
 C39(H39A,H39B,H39C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              5147
_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 0.648