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_1567191
_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_absolute_configuration ad
_chemical_formula_moiety         'C29 H27 N3 O3'
_chemical_formula_sum            'C29 H27 N3 O3'
_chemical_formula_weight         465.53
_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     direct
_audit_creation_date             2021-12-02
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.75496(19)
_cell_length_b                   13.6686(3)
_cell_length_c                   18.7757(4)
_cell_measurement_reflns_used    2614
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.4690
_cell_measurement_theta_min      3.9970
_cell_volume                     2503.49(9)
_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 0.988
_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    -57.00 -32.00   1.00    3.00    --  -33.50 178.00  30.00   25
  2  \w     -6.00  20.00   1.00    3.00    --  -33.50  57.00-120.00   26
  3  \w    -29.00  14.00   1.00    3.00    --  -33.50  37.00-180.00   43
  4  \w    -14.00  30.00   1.00    3.00    --   36.47 -37.00  30.00   44
  5  \w     84.00 110.00   1.00    3.00    --   36.47 178.00-180.00   26
  6  \w     64.00 109.00   1.00    3.00    --   36.47 178.00  90.00   45
  7  \w    -35.00 104.00   1.00    3.00    --   36.47   0.00 -90.00  139
  8  \w     61.00  99.00   1.00   15.00    --  108.00 178.00-180.00   38
  9  \w     39.00 133.00   1.00   15.00    --  108.00 -30.00  60.00   94
 10  \w     57.00 127.00   1.00   15.00    --  108.00 -45.00-180.00   70
 11  \w     51.00  84.00   1.00   15.00    --  108.00 -94.00  30.00   33
 12  \w    125.00 174.00   1.00   15.00    --  108.00 111.00   0.00   49
 13  \w    109.00 161.00   1.00   15.00    --  108.00 111.00  90.00   52
 14  \w     43.00 100.00   1.00   15.00    --  108.00-111.00-120.00   57
 15  \w     39.00 137.00   1.00   15.00    --  108.00 -77.00  60.00   98
;
_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      -0.0402127000
_diffrn_orient_matrix_UB_12      -0.0885080000
_diffrn_orient_matrix_UB_13      -0.0463216000
_diffrn_orient_matrix_UB_21      -0.0445231000
_diffrn_orient_matrix_UB_22      -0.0561169000
_diffrn_orient_matrix_UB_23      0.0672647000
_diffrn_orient_matrix_UB_31      -0.1461758000
_diffrn_orient_matrix_UB_32      0.0413824000
_diffrn_orient_matrix_UB_33      -0.0076973000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0319
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            9409
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.963
_diffrn_reflns_theta_min         4.000
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.648
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96901
_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    1.235
_exptl_crystal_description       block
_exptl_crystal_F_000             984
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.131
_refine_diff_density_min         -0.130
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1281 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.3(2)
_refine_ls_extinction_coef       0.0022(4)
_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   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     320
_refine_ls_number_reflns         4720
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0622
_refine_ls_R_factor_gt           0.0474
_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^)+(0.0656P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1211
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.746
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                3734
_reflns_number_total             4720
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02771b2.cif
_cod_data_source_block           202111339
_cod_depositor_comments
'Adding full bibliography for 1567188--1567191.cif.'
_cod_original_cell_volume        2503.48(8)
_cod_database_code               1567191
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H3O3N2F3
_chemical_oxdiff_usercomment     r
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.903
_reflns_odcompleteness_completeness 99.92
_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:
 C5(H5), C6(H6)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C12(H12), C14(H14), C17(H17), C18(H18), C19(H19), C20(H20),
 C21(H21), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27)
2.c X=CH2 refined with riding coordinates:
 C15(H15A,H15B)
2.d Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C13(H13A,H13B,H13C), C29(H29A,H29B,H29C)
;
_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 1.042
_oxdiff_exptl_absorpt_empirical_full_min 0.947