Ligand-dependent, palladium-catalyzed stereodivergent synthesis of chiral tetrahydroquinolines.
Wang, Yue; Li, Er-Qing; Duan, Zheng; Chemical science 13 (2022) 8131–8136; doi:10.1039/d2sc02771b

data_1567188
_publ_section_title
;
 Ligand-dependent, palladium-catalyzed stereodivergent synthesis of chiral
 tetrahydroquinolines.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              8131
_journal_page_last               8136
_journal_paper_doi               10.1039/d2sc02771b
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C28 H25 N3 O3'
_chemical_formula_sum            'C28 H25 N3 O3'
_chemical_formula_weight         451.51
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-06-16
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-01-05 deposited with the CCDC.	2022-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 130.968(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6477(6)
_cell_length_b                   12.7165(3)
_cell_length_c                   19.2801(10)
_cell_measurement_reflns_used    3839
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.1000
_cell_measurement_theta_min      4.6090
_cell_volume                     2341.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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   -108.00 -51.00   1.00    4.00    --  -33.50 178.00-180.00   57
  2  \w    -97.00 -32.00   1.00    4.00    --  -33.50 -57.00 -60.00   65
  3  \w     60.00 105.00   1.00    4.00    --   36.47  77.00 -30.00   45
  4  \w     34.00  59.00   1.00    4.00    --   36.47 -37.00  30.00   25
  5  \w     34.00 104.00   1.00    4.00    --   36.47  37.00-120.00   70
  6  \w    -34.00   9.00   1.00    4.00    --   36.47 -37.00  30.00   43
  7  \w     57.00 107.00   1.00    4.00    --   36.47 178.00 150.00   50
  8  \w     76.00 106.00   1.00    4.00    --   36.47 178.00 -90.00   30
  9  \w     84.00 110.00   1.00    4.00    --   36.47 178.00 120.00   26
 10  \w     10.00  36.00   1.00    4.00    --   36.47  77.00 -30.00   26
 11  \w     42.00 107.00   1.00   13.00    --  108.00 -94.00  30.00   65
 12  \w     93.00 119.00   1.00   13.00    --  108.00  45.00   0.00   26
 13  \w    150.00 178.00   1.00   15.00    --  108.00  45.00   0.00   28
 14  \w    102.00 128.00   1.00   15.00    --  108.00 112.00  22.00   26
 15  \w     38.00 103.00   1.00   15.00    --  108.00 -30.00  90.00   65
 16  \w     83.00 109.00   1.00   15.00    --  108.00 -94.00-120.00   26
 17  \w     38.00  78.00   1.00   15.00    --  108.00 -94.00-120.00   40
 18  \w     42.00 123.00   1.00   15.00    --  108.00 -30.00   0.00   81
 19  \w     42.00 128.00   1.00   15.00    --  108.00 -77.00  90.00   86
 20  \w   -101.00 -57.00   1.00    3.00    --  -33.50 -37.00-120.00   44
 21  \w     14.00  40.00   1.00    3.00    --   36.47 -57.00   0.00   26
 22  \w    -17.00  25.00   1.00    3.00    --   36.47 -77.00 150.00   42
 23  \w     57.00  82.00   1.00    3.00    --   36.47 178.00   0.00   25
 24  \w    108.00 134.00   1.00   15.00    --  108.00 -77.00  30.00   26
 25  \w     57.00  83.00   1.00   15.00    --  108.00 -77.00  30.00   26
 26  \w     97.00 123.00   1.00   15.00    --  108.00  61.00-120.00   26
 27  \w     92.00 171.00   1.00   15.00    --  108.00  45.00 -90.00   79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0517387000
_diffrn_orient_matrix_UB_12      -0.0304161000
_diffrn_orient_matrix_UB_13      0.0952537000
_diffrn_orient_matrix_UB_21      -0.1527902000
_diffrn_orient_matrix_UB_22      -0.0141542000
_diffrn_orient_matrix_UB_23      -0.0418060000
_diffrn_orient_matrix_UB_31      0.0052202000
_diffrn_orient_matrix_UB_32      -0.1163494000
_diffrn_orient_matrix_UB_33      -0.0197489000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0320
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            11047
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         4.617
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.677
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87748
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.281
_exptl_crystal_description       block
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.247
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.037
_refine_ls_extinction_coef       0.0043(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     310
_refine_ls_number_reflns         4178
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0460
_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^)+(0.0687P)^2^+0.3656P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1212
_refine_ls_wR_factor_ref         0.1326
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3373
_reflns_number_total             4178
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02771b2.cif
_cod_data_source_block           202106165a
_cod_depositor_comments
'Adding full bibliography for 1567188--1567191.cif.'
_cod_database_code               1567188
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O5N2
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.905
_reflns_odcompleteness_completeness 99.93
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C13(H13), C16(H16), C17(H17), C18(H18),
 C19(H19), C20(H20), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28)
2.c X=CH2 refined with riding coordinates:
 C14(H14A,H14B)
2.d Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              18148
_shelx_hkl_checksum              40665
_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 1.386
_oxdiff_exptl_absorpt_empirical_full_min 0.904