Diastereoselective construction of bridged piperidines through an interrupted dearomative reduction
Han, Huabin; Wang, Lele; Niu, Xinyue; Li, Chaoyang; Xu, Yuanqing; Wang, Qilin; Chemical Communications  (2022) –; doi:10.1039/D2CC02225G

data_7130286
_publ_section_title
;
 Diastereoselective construction of bridged piperidines through an
 interrupted dearomative reduction
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC02225G
_journal_year                    2022
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H20 N2 O3'
_chemical_formula_sum            'C21 H20 N2 O3'
_chemical_formula_weight         348.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-12-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-03-29 deposited with the CCDC.	2022-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 121.241(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.6978(5)
_cell_length_b                   7.32067(11)
_cell_length_c                   12.3466(3)
_cell_measurement_reflns_used    3360
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8710
_cell_measurement_theta_min      4.5490
_cell_volume                     1754.06(8)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -42.00  -5.00   0.50    2.00    --  -33.50 -77.00 -60.00   74
  2  \w    -83.00 -58.00   0.50    2.00    --  -33.50 -57.00-180.00   50
  3  \w   -101.00 -61.00   0.50    2.00    --  -33.50 -77.00 -60.00   80
  4  \w     61.00  99.00   0.50    2.00    --   36.47 178.00  90.00   76
  5  \w     73.00 110.00   0.50    2.00    --   36.47 178.00  30.00   74
  6  \w     14.00  54.00   0.50    2.00    --   36.47  77.00 150.00   80
  7  \w     63.00 110.00   0.50    2.00    --   36.47 178.00 -60.00   94
  8  \w     55.00 103.00   0.50    2.00    --   36.47  37.00 150.00   96
  9  \w     52.00  77.00   0.50    2.00    --   36.47 -99.00 -30.00   50
 10  \w     -3.00  32.00   0.50    2.00    --   36.47 -99.00 -30.00   70
 11  \w      0.00  69.00   0.50    2.00    --   36.47  19.00 -90.00  138
 12  \w     24.00  58.00   0.50    2.00    --   36.47  37.00 120.00   68
 13  \w     64.00  97.00   0.50    2.00    --   36.47 178.00 -90.00   66
 14  \w    -31.00  49.00   0.50    2.00    --   36.47 -57.00-180.00  160
 15  \w     81.00 106.00   0.50    2.00    --   36.47  77.00 150.00   50
 16  \w     20.00  47.00   0.50    2.00    --   36.47  57.00-120.00   54
 17  \w     75.00 105.00   0.50    2.00    --   36.47  57.00 -90.00   60
 18  \w     -1.00 108.00   0.50    2.00    --   36.47  19.00 120.00  218
 19  \w     37.00  64.00   0.50    2.00    --   36.47  57.00 120.00   54
 20  \w     79.00 106.00   0.50    6.50    --  108.00  77.00  90.00   54
 21  \w     88.00 114.00   0.50    6.50    --  108.00  61.00-180.00   52
 22  \w     78.00 134.00   0.50    6.50    --  108.00 -77.00 -30.00  112
 23  \w     85.00 139.00   0.50    6.50    --  108.00  30.00 120.00  108
 24  \w     39.00  76.00   0.50    6.50    --  108.00 -77.00 -30.00   74
 25  \w     82.00 135.00   0.50    6.50    --  108.00  30.00 150.00  106
 26  \w     82.00 109.00   0.50    6.50    --  108.00  30.00-180.00   54
 27  \w    108.00 176.00   0.50    6.50    --  108.00 111.00 -60.00  136
 28  \w    147.00 174.00   0.50    6.50    --  108.00  61.00-150.00   54
 29  \w     88.00 114.00   0.50    6.50    --  108.00  61.00 150.00   52
 30  \w     62.00 119.00   0.50    6.50    --  108.00 -61.00-150.00  114
 31  \w     89.00 140.00   0.50    6.50    --  108.00  61.00-150.00  102
 32  \w    123.00 176.00   0.50    6.50    --  108.00  77.00 150.00  106
 33  \w     88.00 115.00   0.50    6.50    --  108.00  45.00 150.00   54
 34  \w     79.00 105.00   0.50    6.50    --  108.00  77.00 150.00   52
 35  \w     80.00 106.00   0.50    6.50    --  108.00  77.00 120.00   52
 36  \w     82.00 108.00   0.50    6.50    --  108.00  30.00-150.00   52
 37  \w    122.00 170.00   0.50    6.50    --  108.00  77.00-180.00   96
 38  \w     88.00 135.00   0.50    6.50    --  108.00  45.00  90.00   94
 39  \w    133.00 175.00   0.50    6.50    --  108.00  30.00-120.00   84
 40  \w     79.00 106.00   0.50    6.50    --  108.00  77.00-180.00   54
 41  \w     83.00 111.00   0.50    6.50    --  108.00  30.00-120.00   56
 42  \w     88.00 115.00   0.50    6.50    --  108.00  61.00 120.00   54
 43  \w     89.00 114.00   0.50    6.50    --  108.00  45.00-150.00   50
 44  \w    153.00 178.00   0.50    6.50    --  108.00 102.00 -92.00   50
 45  \w     42.00 110.00   0.50    6.50    --  108.00 -94.00-120.00  136
 46  \w     37.00 133.00   0.50    6.50    --  108.00 -30.00-150.00  192
;
_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      0.0614456776
_diffrn_orient_matrix_UB_12      -0.0984463587
_diffrn_orient_matrix_UB_13      0.1118490831
_diffrn_orient_matrix_UB_21      0.0442575144
_diffrn_orient_matrix_UB_22      0.0387640807
_diffrn_orient_matrix_UB_23      -0.0588176485
_diffrn_orient_matrix_UB_31      0.0238120111
_diffrn_orient_matrix_UB_32      0.1818887514
_diffrn_orient_matrix_UB_33      0.0730188282
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0220
_diffrn_reflns_av_unetI/netI     0.0212
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            6852
_diffrn_reflns_point_group_measured_fraction_full 0.753
_diffrn_reflns_point_group_measured_fraction_max 0.753
_diffrn_reflns_theta_full        67.059
_diffrn_reflns_theta_max         67.059
_diffrn_reflns_theta_min         6.462
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.720
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85145
_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    1.319
_exptl_crystal_description       block
_exptl_crystal_F_000             736
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.123
_refine_diff_density_min         -0.153
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 725 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.20(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     235
_refine_ls_number_reflns         2357
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0351
_refine_ls_R_factor_gt           0.0338
_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^)+(0.0540P)^2^+0.3564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0893
_refine_ls_wR_factor_ref         0.0911
_reflns_Friedel_coverage         0.505
_reflns_Friedel_fraction_full    0.506
_reflns_Friedel_fraction_max     0.506
_reflns_number_gt                2272
_reflns_number_total             2357
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02225g2.cif
_cod_data_source_block           wll142
_cod_original_cell_volume        1754.07(8)
_cod_database_code               7130286
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H40O2N4
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.900
_reflns_odcompleteness_completeness 99.94
_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
2.a Ternary CH refined with riding coordinates:
 C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C5(H5A,H5B), C6(H6A,H6B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21)
;
_shelx_res_checksum              76449
_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 1.285
_oxdiff_exptl_absorpt_empirical_full_min 0.893