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_7130288
_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_formula_moiety         'C22 H22 N2 O3'
_chemical_formula_sum            'C22 H22 N2 O3'
_chemical_formula_weight         362.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-01-04
_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                 99.363(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3385(5)
_cell_length_b                   7.6142(3)
_cell_length_c                   19.6850(8)
_cell_measurement_reflns_used    3387
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.4460
_cell_measurement_theta_min      5.3280
_cell_volume                     1824.72(13)
_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 1.000
_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     -3.00  23.00   1.00    1.50    --  -33.50  77.00  60.00   26
  2  \w   -103.00 -12.00   1.00    1.50    --  -33.50 -37.00 -90.00   91
  3  \w    -35.00  -9.00   1.00    1.50    --  -33.50  77.00  60.00   26
  4  \w     78.00 103.00   1.00    1.50    --   36.47  77.00 -90.00   25
  5  \w     66.00  92.00   1.00    1.50    --   36.47  37.00  30.00   26
  6  \w     24.00  53.00   1.00    1.50    --   36.47 -37.00 -90.00   29
  7  \w     19.00  83.00   1.00    1.50    --   36.47  57.00  60.00   64
  8  \w     10.00  60.00   1.00    1.50    --   36.47  77.00 -90.00   50
  9  \w    -13.00  14.00   1.00    1.50    --   36.47 -37.00 -90.00   27
 10  \w     64.00 109.00   1.00    1.50    --   36.47 178.00-120.00   45
 11  \w     58.00  87.00   1.00    1.50    --   36.47 178.00-150.00   29
 12  \w     16.00  65.00   1.00    1.50    --   36.47  37.00  30.00   49
 13  \w     58.00 106.00   1.00    1.50    --   36.47 178.00 -60.00   48
 14  \w     -4.00  22.00   1.00    1.50    --   36.47 102.00  64.60   26
 15  \w     23.00  98.00   1.00    1.50    --   36.47  57.00  90.00   75
 16  \w     28.00 105.00   1.00    1.50    --   36.47  57.00-180.00   77
 17  \w     88.00 147.00   1.00    6.00    --  108.00  61.00  30.00   59
 18  \w     76.00 108.00   1.00    6.00    --  108.00 -94.00-180.00   32
 19  \w     40.00 127.00   1.00    6.00    --  108.00 -61.00 120.00   87
 20  \w    139.00 166.00   1.00    6.00    --  108.00  61.00 120.00   27
 21  \w     90.00 116.00   1.00    6.00    --  108.00  45.00 120.00   26
 22  \w     44.00 133.00   1.00    6.00    --  108.00 -30.00-180.00   89
 23  \w     79.00 105.00   1.00    6.00    --  108.00  77.00 150.00   26
 24  \w     90.00 117.00   1.00    6.00    --  108.00  61.00 120.00   27
 25  \w     82.00 108.00   1.00    6.00    --  108.00  30.00-180.00   26
 26  \w     82.00 125.00   1.00    6.00    --  108.00  30.00 120.00   43
 27  \w     84.00 133.00   1.00    6.00    --  108.00  30.00-150.00   49
 28  \w     65.00  93.00   1.00    6.00    --  108.00  15.00-150.00   28
 29  \w     38.00  92.00   1.00    6.00    --  108.00 -94.00   0.00   54
 30  \w     88.00 114.00   1.00    6.00    --  108.00  61.00-180.00   26
 31  \w     38.00  97.00   1.00    6.00    --  108.00 -94.00 120.00   59
 32  \w    126.00 173.00   1.00    6.00    --  108.00  30.00  60.00   47
 33  \w     79.00 105.00   1.00    6.00    --  108.00  77.00 120.00   26
 34  \w     87.00 160.00   1.00    6.00    --  108.00  30.00   0.00   73
 35  \w     88.00 114.00   1.00    6.00    --  108.00  45.00-180.00   26
 36  \w     89.00 115.00   1.00    6.00    --  108.00  61.00 150.00   26
 37  \w     85.00 110.00   1.00    6.00    --  108.00  30.00 150.00   25
 38  \w    137.00 176.00   1.00    6.00    --  108.00  61.00-180.00   39
 39  \w    114.00 174.00   1.00    6.00    --  108.00  77.00 150.00   60
 40  \w     73.00 131.00   1.00    6.00    --  108.00 -77.00-150.00   58
 41  \w     82.00 120.00   1.00    6.00    --  108.00  77.00-150.00   38
;
_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      0.0532521000
_diffrn_orient_matrix_UB_12      0.1487839000
_diffrn_orient_matrix_UB_13      0.0470053000
_diffrn_orient_matrix_UB_21      -0.0835345000
_diffrn_orient_matrix_UB_22      -0.0309474000
_diffrn_orient_matrix_UB_23      0.0490366000
_diffrn_orient_matrix_UB_31      0.0787247000
_diffrn_orient_matrix_UB_32      -0.1335110000
_diffrn_orient_matrix_UB_33      0.0409987000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            13564
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.631
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.712
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87980
_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             768
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.164
_refine_diff_density_min         -0.194
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3260
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0429
_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^)+(0.0608P)^2^+0.2745P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1105
_refine_ls_wR_factor_ref         0.1198
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2641
_reflns_number_total             3260
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc02225g2.cif
_cod_data_source_block           hhb36
_cod_original_cell_volume        1824.71(13)
_cod_database_code               7130288
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H40O2N4
_shelx_estimated_absorpt_t_max   0.945
_shelx_estimated_absorpt_t_min   0.907
_reflns_odcompleteness_completeness 99.97
_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. Rigid bond restraints
 N2, C18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(N2) \\sim Ueq, Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C9(H9)
4.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C16(H16A,H16B), C17(H17A,H17B), C21(H21A,H21B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13),
 C14(H14), C20(H20)
4.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_shelx_res_checksum              52688
_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 1.204
_oxdiff_exptl_absorpt_empirical_full_min 0.869