Pd-catalyzed enantioselective access to hydrocarbazolones containing contiguous quaternary and tertiary stereocenters
Sun, Hao; Yu, Cheng-Long; Zheng, Yu-Qing; Shu, Peng-Fei; Dong, Zhan; Xia, Yu-Chen; Liu, Wen-Bo; Chemical Science 16 (2025) 6425–6433; doi:10.1039/D4SC08215J

data_1574097
_publ_section_title
;
 Pd-catalyzed enantioselective access to hydrocarbazolones containing
 contiguous quaternary and tertiary stereocenters
;
_journal_issue                   15
_journal_name_full               'Chemical Science'
_journal_page_first              6425
_journal_page_last               6433
_journal_paper_doi               10.1039/D4SC08215J
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H17 N O'
_chemical_formula_sum            'C14 H17 N O'
_chemical_formula_weight         215.28
_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_block_doi                 10.5517/ccdc.csd.cc2kbpyk
_audit_creation_date             2022-03-30
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-07-03 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.3450(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.04600(10)
_cell_length_b                   18.2634(2)
_cell_length_c                   8.55970(10)
_cell_measurement_reflns_used    12925
_cell_measurement_temperature    249.97(10)
_cell_measurement_theta_max      69.3190
_cell_measurement_theta_min      4.7950
_cell_volume                     1193.90(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      249.97(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.984
_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    -89.00  89.00   0.50    0.50    --    0.00  13.00 -58.00  356
  2  \w   -182.00  -3.00   0.50    0.50    --  -92.30 -13.00 129.00  358
  3  \w   -182.00  -3.00   0.50    0.50    --  -92.30  13.00 -58.00  358
  4  \w    -33.00  89.00   0.50    0.50    --    0.00  57.00  60.00  244
  5  \w    -32.00  94.00   0.50    0.50    --    5.00  38.00  90.00  252
  6  \w    -27.00  94.00   0.50    0.50    --    5.00  51.00 -16.78  242
  7  \w    -84.00  94.00   0.50    0.50    --    5.00  13.00 -58.00  356
  8  \w    -84.00  42.00   0.50    0.50    --    5.00 -38.00   0.00  252
  9  \w   -182.00 -54.00   0.50    0.50    --  -92.30 -76.00  75.24  256
 10  \w   -160.00 -54.00   0.50    0.50    --  -92.30 -76.00 120.00  212
 11  \w    -45.00 -18.00   0.50    0.50    --  -92.30  76.00  30.00   54
 12  \w    -82.00 -56.00   0.50    0.50    --  -92.30 -72.00  94.59   52
 13  \w    -80.00 -54.00   0.50    0.50    --  -92.30 -76.00  60.00   52
 14  \w   -182.00 -58.00   0.50    0.50    --  -92.30 -63.00  -8.73  248
 15  \w    -86.00 -60.00   0.50    0.50    --  -92.30 -52.00   3.35   52
 16  \w   -182.00 -69.00   0.50    0.50    --  -92.30 -57.00  90.00  226
 17  \w   -131.00  -3.00   0.50    0.50    --  -92.30  76.00  90.00  256
 18  \w    -80.00 -54.00   0.50    0.50    --  -92.30 -76.00  30.00   52
 19  \w    -82.00 -57.00   0.50    0.50    --  -92.30 -42.00  90.31   50
 20  \w    -82.00 -56.00   0.50    0.50    --  -92.30 -73.00  -9.17   52
 21  \w    -80.00 -54.00   0.50    0.50    --  -92.30 -76.00  51.77   52
 22  \w   -121.00 -92.00   0.50    0.50    --  -92.30 -42.00  90.31   58
 23  \w   -159.00-133.00   0.50    0.50    --  -92.30 -66.00  21.02   52
 24  \w    -82.00 -57.00   0.50    0.50    --  -92.30 -66.00  21.02   50
 25  \w   -172.00-146.00   0.50    0.50    --  -92.30 -39.00 -19.88   52
 26  \w   -119.00 -55.00   0.50    0.50    --  -92.30 -39.00 -19.88  128
 27  \w    -91.00 -54.00   0.50    0.50    --  -92.30 -76.00 -30.00   74
 28  \w    -94.00 -10.00   0.50    0.50    --  -92.30  57.00  90.00  168
 29  \w    -85.00 -58.00   0.50    0.50    --  -92.30 -67.00  -6.28   54
 30  \w    -84.00 -59.00   0.50    0.50    --  -92.30 -57.00  60.00   50
 31  \w    -86.00 -59.00   0.50    0.50    --  -92.30 -57.00  -3.43   54
 32  \w    -85.00 -59.00   0.50    0.50    --  -92.30 -57.00  41.74   52
 33  \w   -125.00 -96.00   0.50    0.50    --  -92.30  57.00  90.00   58
 34  \w    -82.00 -56.00   0.50    0.50    --  -92.30 -69.00  53.08   52
 35  \w   -182.00 -55.00   0.50    0.50    --  -92.30 -38.00  30.00  254
 36  \w   -168.00-131.00   0.50    0.50    --  -92.30 -76.00  30.00   74
 37  \w   -107.00 -82.00   0.50    0.50    --  -92.30  76.00  30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1983129000
_diffrn_orient_matrix_UB_12      -0.0119682000
_diffrn_orient_matrix_UB_13      0.0791648000
_diffrn_orient_matrix_UB_21      -0.0261588000
_diffrn_orient_matrix_UB_22      -0.0093066000
_diffrn_orient_matrix_UB_23      0.1696578000
_diffrn_orient_matrix_UB_31      -0.0257394000
_diffrn_orient_matrix_UB_32      -0.0829715000
_diffrn_orient_matrix_UB_33      -0.0304465000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0193
_diffrn_reflns_av_unetI/netI     0.0137
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            20575
_diffrn_reflns_point_group_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.435
_diffrn_reflns_theta_min         4.843
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92818
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
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    1.198
_exptl_crystal_description       block
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.120
_refine_diff_density_min         -0.090
_refine_diff_density_rms         0.021
_refine_ls_abs_structure_details
;
 Flack x determined using 1909 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4294
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0276
_refine_ls_R_factor_gt           0.0269
_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^)+(0.0456P)^2^+0.0662P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0732
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    0.951
_reflns_Friedel_fraction_max     0.925
_reflns_number_gt                4186
_reflns_number_total             4294
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08215j2.cif
_cod_data_source_block           lwb-ycl-iii-088-20220329-250k
_cod_depositor_comments
'Adding full bibliography for 1574097--1574098.cif.'
_cod_database_code               1574097
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C H  N O'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.955
_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:
 C26(H26), C12(H12)
2.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C25(H25A,H25B), C9(H9A,H9B), C23(H23A,H23B), C11(H11A,H11B),
 C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C17(H17), C16(H16), C18(H18), C19(H19), C5(H5), C4(H4), C2(H2), C3(H3)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C27(H27A,H27B,H27C), C13(H13A,H13B,H13C), C28(H28A,H28B,
 H28C)
;
_shelx_res_checksum              44267
_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 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.907