Access to chiral dihydrophenanthridines <i>via</i> a palladium(0)-catalyzed Suzuki coupling and C-H arylation cascade reaction using new chiral-bridged biphenyl bifunctional ligands.
Chen, Bin; Pan, Bendu; He, Xiaobo; Jiang, Long; Chan, Albert S. C.; Qiu, Liqin; Chemical science 15 (2024) 6884–6890; doi:10.1039/d4sc00621f

data_1571375
_publ_section_title
;
 Access to chiral dihydrophenanthridines <i>via</i> a
 palladium(0)-catalyzed Suzuki coupling and C-H arylation cascade reaction
 using new chiral-bridged biphenyl bifunctional ligands.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              6884
_journal_page_last               6890
_journal_paper_doi               10.1039/d4sc00621f
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H25 N O2, 0.08(H2 O1)'
_chemical_formula_sum            'C25 H25.17 N O2.08'
_chemical_formula_weight         372.96
_space_group_crystal_system      trigonal
_space_group_IT_number           152
_space_group_name_Hall           'P 31 2"'
_space_group_name_H-M_alt        'P 31 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-11-14 deposited with the CCDC.	2024-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   11.43405(6)
_cell_length_b                   11.43405(6)
_cell_length_c                   25.89293(13)
_cell_measurement_reflns_used    39378
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.0070
_cell_measurement_theta_min      4.4180
_cell_volume                     2931.65(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.972
_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      2.00  27.00   1.00    2.00    --   38.00  90.00-156.35   25
  2  \w    -98.00 -19.00   1.00    2.00    --  -41.94 -38.00-180.00   79
  3  \w   -112.00 -15.00   1.00    2.00    --  -41.94 -57.00 120.00   97
  4  \w   -101.00 -74.00   1.00    2.00    --  -41.94 -57.00 -30.00   27
  5  \w    -67.00 -17.00   1.00    2.00    --  -41.94 -57.00 -30.00   50
  6  \w   -118.00  -6.00   1.00    2.00    --  -41.94 -19.00 -90.00  112
  7  \w      6.00  81.00   1.00    2.00    --   41.94 -99.00   0.00   75
  8  \w     10.00  35.00   1.00    2.00    --   41.94  78.00 -42.18   25
  9  \w     27.00  94.00   1.00    2.00    --   41.94-125.00-150.00   67
 10  \w     14.00  39.00   1.00    2.00    --   46.00  81.00   0.50   25
 11  \w     13.00  38.00   1.00    2.00    --   46.00  82.00-156.35   25
 12  \w     14.00  42.00   1.00    2.00    --   46.00  81.00  55.05   28
 13  \w     13.00  38.00   1.00    2.00    --   46.00  82.00  91.46   25
 14  \w     25.00  54.00   1.00    2.00    --   54.00  71.00-108.66   29
 15  \w     83.00 129.00   1.00    2.00    --   58.00  70.00  18.19   46
 16  \w     28.00  54.00   1.00    2.00    --   58.00  70.00  18.19   26
 17  \w     29.00  54.00   1.00    2.00    --   58.00  71.00 140.60   25
 18  \w    101.00 130.00   1.00    2.00    --   58.00  71.00 140.60   29
 19  \w     37.00  62.00   1.00    2.00    --   66.00  70.00 -47.60   25
 20  \w    108.00 134.00   1.00    2.00    --   66.00  70.00 -47.60   26
 21  \w     37.00  62.00   1.00    2.00    --   66.00  69.00 -72.16   25
 22  \w     36.00  62.00   1.00    2.00    --   66.00  71.00 151.49   26
 23  \w     41.00  70.00   1.00    2.00    --   70.00  69.00-125.01   29
 24  \w     40.00  66.00   1.00    2.00    --   70.00  70.00  92.44   26
 25  \w    105.00 131.00   1.00    2.00    --   70.00  70.00-159.10   26
 26  \w    116.00 142.00   1.00    2.00    --   70.00  70.00  33.06   26
 27  \w     40.00  66.00   1.00    2.00    --   70.00  70.00-159.10   26
 28  \w     43.00  68.00   1.00    2.00    --   70.00  64.00-176.14   25
 29  \w     40.00  66.00   1.00    2.00    --   70.00  70.00  33.06   26
 30  \w     44.00  78.00   1.00    2.00    --   74.00  71.00 121.27   34
 31  \w     94.00 120.00   1.00    2.00    --   74.00  71.00 121.27   26
 32  \w     46.00  74.00   1.00    2.00    --   74.00  64.00 -17.42   28
 33  \w     48.00  74.00   1.00    8.00    --   78.00  70.00  43.71   26
 34  \w    134.00 160.00   1.00    8.00    --   90.00  68.00  41.85   26
 35  \w     60.00  93.00   1.00    8.00    --   90.00  70.00-108.20   33
 36  \w     61.00  94.00   1.00    8.00    --   90.00  68.00  41.85   33
 37  \w     64.00  90.00   1.00    8.00    --   90.00  56.00   9.55   26
 38  \w    102.00 161.00   1.00    8.00    --   90.00  69.00-139.78   59
 39  \w     61.00  89.00   1.00    8.00    --   90.00  69.00-139.78   28
 40  \w     62.00  93.00   1.00    8.00    --   90.00  62.00 -48.57   31
 41  \w     70.00  96.00   1.00    8.00    --   94.00  46.00  -3.66   26
 42  \w     66.00  97.00   1.00    8.00    --   94.00  61.00 103.15   31
 43  \w     67.00 101.00   1.00    8.00    --   94.00  57.00 167.09   34
 44  \w    146.00 172.00   1.00    8.00    --  106.00  65.00 -22.41   26
 45  \w     78.00 125.00   1.00    8.00    --  106.00  65.00 -22.41   47
 46  \w     33.00 104.00   1.00    8.00    --  111.00 -94.00 -60.00   71
 47  \w     83.00 175.00   1.00    8.00    --  111.00  61.00  90.00   92
 48  \w     42.00 107.00   1.00    8.00    --  111.00-111.00 150.00   65
 49  \w     84.00 171.00   1.00    8.00    --  111.00  61.00  30.00   87
 50  \w    143.00 171.00   1.00    8.00    --  111.00  61.00   0.00   28
 51  \w     84.00 140.00   1.00    8.00    --  111.00  61.00   0.00   56
 52  \w    115.00 172.00   1.00    8.00    --  111.00  61.00-150.00   57
 53  \w     83.00 112.00   1.00    8.00    --  111.00  61.00-150.00   29
 54  \w     83.00 156.00   1.00    8.00    --  111.00  61.00-180.00   73
 55  \w     47.00  74.00   1.00    8.00    --  111.00 -94.00 -30.00   27
 56  \w     83.00 154.00   1.00    8.00    --  111.00  61.00 -60.00   71
 57  \w    141.00 176.00   1.00    8.00    --  111.00  61.00 120.00   35
 58  \w     83.00 135.00   1.00    8.00    --  111.00  61.00 120.00   52
 59  \w     44.00 109.00   1.00    8.00    --  111.00-111.00 -90.00   65
 60  \w     41.00 109.00   1.00    8.00    --  111.00-111.00  90.00   68
 61  \w     84.00 112.00   1.00    8.00    --  111.00  61.00-120.00   28
 62  \w    115.00 166.00   1.00    8.00    --  111.00  61.00-120.00   51
 63  \w     83.00 163.00   1.00    8.00    --  111.00  61.00  60.00   80
 64  \w     39.00  75.00   1.00    8.00    --  111.00-111.00  60.00   36
 65  \w    109.00 177.00   1.00    8.00    --  111.00 111.00 -60.00   68
 66  \w     45.00  82.00   1.00    8.00    --  111.00-111.00 120.00   37
 67  \w     83.00 172.00   1.00    8.00    --  111.00  61.00 150.00   89
 68  \w     48.00 109.00   1.00    8.00    --  111.00-111.00  30.00   61
 69  \w     83.00 178.00   1.00    8.00    --  111.00  61.00 -90.00   95
 70  \w     83.00 108.00   1.00    8.00    --  111.00-111.00-180.00   25
 71  \w     44.00  73.00   1.00    8.00    --  111.00-111.00-180.00   29
 72  \w     50.00 103.00   1.00    8.00    --  111.00-111.00-120.00   53
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0103759000
_diffrn_orient_matrix_UB_12      0.1063135000
_diffrn_orient_matrix_UB_13      -0.0391012000
_diffrn_orient_matrix_UB_21      -0.0262009000
_diffrn_orient_matrix_UB_22      -0.0994663000
_diffrn_orient_matrix_UB_23      -0.0445660000
_diffrn_orient_matrix_UB_31      -0.1530016000
_diffrn_orient_matrix_UB_32      -0.0548344000
_diffrn_orient_matrix_UB_33      0.0049746000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0614
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            57622
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.125
_diffrn_reflns_theta_min         4.465
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.628
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73457
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
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    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             1193
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.155
_refine_diff_density_min         -0.143
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1666 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(6)
_refine_ls_extinction_coef       0.00057(18)
_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   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     268
_refine_ls_number_reflns         3980
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0275
_refine_ls_R_factor_gt           0.0272
_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^)+(0.0513P)^2^+0.2475P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0729
_refine_ls_wR_factor_ref         0.0733
_reflns_Friedel_coverage         0.740
_reflns_Friedel_fraction_full    0.977
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                3934
_reflns_number_total             3980
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00621f2.cif
_cod_data_source_block           a23101302aqlq
_cod_depositor_comments          'Adding full bibliography for 1571375.cif.'
_cod_database_code               1571375
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C25H25.2NO2.1
_chemical_oxdiff_usercomment     371
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.912
_diffrn_oxdiff_digest_frames
;
0147483cd1f0d7435140473481e48cb6a5032715934
;
_diffrn_oxdiff_digest_hkl
;
01ddb8f28627720fd303f5a17c6f2f3bd68c49
;
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
3. Others
 Fixed Sof: O3(0.08333) H3a(0.08333) H3b(0.08333)
4.a Riding coordinates:
 O3(H3a,H3b)
4.b Ternary CH refined with riding coordinates:
 C1(H1)
4.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15), C17(H17),
 C19(H19)
4.d Idealised Me refined as rotating group:
 C21(H21a,H21b,H21c), C22(H22a,H22b,H22c), C23(H23a,H23b,H23c), C24(H24a,H24b,
 H24c), C25(H25a,H25b,H25c)
;
_shelx_res_checksum              94162
_olex2_date_sample_data_collection 2023-10-13
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.408
_oxdiff_exptl_absorpt_empirical_full_min 0.743