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_1567189
_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         '0.25(C41 H41 N P2 S)'
_chemical_formula_sum            'C11 H10 N O P S'
_chemical_formula_weight         235.23
_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             2022-01-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-08 deposited with the CCDC.	2022-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.2740(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   8.80910(10)
_cell_length_b                   14.29220(10)
_cell_length_c                   15.6275(2)
_cell_measurement_reflns_used    11999
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      73.5410
_cell_measurement_theta_min      4.2110
_cell_volume                     1951.69(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (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      200.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_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     52.00  89.00   0.50    0.50    --    0.00  57.00 150.00   74
  2  \w    -17.00  73.00   0.50    0.50    --    0.00  38.00 -90.00  180
  3  \w    -88.00  29.00   0.50    0.50    --    0.00 -38.00 -90.00  234
  4  \w    -27.00  48.00   0.50    0.50    --    0.00  57.00 150.00  150
  5  \w     17.00  44.00   0.50    0.50    --    0.00  57.00 -30.00   54
  6  \w     17.00 136.00   0.50    1.60    --   98.80 -82.00   0.00  238
  7  \w     78.00 109.00   0.50    1.60    --   98.80 -82.00 -90.00   62
  8  \w     14.00 128.00   0.50    1.60    --   98.80 -61.00 150.00  228
  9  \w     19.00  65.00   0.50    1.60    --   98.80 -82.00 -90.00   92
 10  \w    112.00 144.00   0.50    1.60    --   98.80  61.00-150.00   64
 11  \w     73.00  99.00   0.50    1.60    --   98.80 -82.00  30.00   52
 12  \w     83.00 108.00   0.50    1.60    --   98.80 -82.00  60.00   50
 13  \w    136.00 186.00   0.50    1.60    --   98.80  30.00   0.00  100
 14  \w    162.00 188.00   0.50    1.60    --   98.80  30.00 120.00   52
 15  \w     75.00 127.00   0.50    1.60    --   98.80 -45.00-150.00  104
 16  \w     11.00  66.00   0.50    1.60    --   98.80 -45.00-150.00  110
 17  \w     10.00 128.00   0.50    1.60    --   98.80 -61.00   0.00  236
 18  \w     80.00 106.00   0.50    1.60    --   98.80  61.00-150.00   52
 19  \w     65.00 144.00   0.50    1.60    --   98.80  30.00 120.00  158
 20  \w     66.00 114.00   0.50    1.60    --   98.80  30.00   0.00   96
 21  \w     81.00 121.00   0.50    1.60    --   98.80 -82.00-150.00   80
 22  \w     61.00  94.00   0.50    1.60    --   98.80 -82.00 -60.00   66
 23  \w     12.00 127.00   0.50    1.60    --   98.80 -82.00 150.00  230
 24  \w     72.00  97.00   0.50    1.60    --   98.80 -82.00 120.00   50
 25  \w     46.00 183.00   0.50    1.60    --   98.80  15.00  90.00  274
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1591296000
_diffrn_orient_matrix_UB_12      0.0454171000
_diffrn_orient_matrix_UB_13      0.0030076000
_diffrn_orient_matrix_UB_21      -0.0296512000
_diffrn_orient_matrix_UB_22      0.0177140000
_diffrn_orient_matrix_UB_23      -0.0979036000
_diffrn_orient_matrix_UB_31      -0.0698681000
_diffrn_orient_matrix_UB_32      0.0961619000
_diffrn_orient_matrix_UB_33      0.0166664000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0321
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            20108
_diffrn_reflns_point_group_measured_fraction_full 0.908
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.720
_diffrn_reflns_theta_min         2.851
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.231
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69391
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.601
_exptl_crystal_description       plate
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.369
_refine_diff_density_min         -0.287
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 2485 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.036(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     409
_refine_ls_number_reflns         6966
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0685P)^2^+0.3551P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1134
_refine_ls_wR_factor_ref         0.1146
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    0.807
_reflns_Friedel_fraction_max     0.766
_reflns_number_gt                6571
_reflns_number_total             6966
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02771b2.cif
_cod_data_source_block           exp_9879
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_absolute_configuration' value 'AD' was changed
to 'ad' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1567188--1567191.cif.
;
_cod_database_code               1567189
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.677
_shelx_estimated_absorpt_t_min   0.363
_reflns_odcompleteness_completeness 100.00
_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:
 C13(H13), C20(H20), C22(H22)
2.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C1(H1A), C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17),
  C18(H18), C19(H19), C25(H25), C26(H26), C27(H27), C28(H28), C31(H31),
 C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40),
  C41(H41)
2.d Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C12(H12A,H12B,H12C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              36131
_shelx_hkl_checksum              94364
_shelx_fab_checksum              11441
_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 1.278
_oxdiff_exptl_absorpt_empirical_full_min 0.728