A Stereospecific Total Synthesis of dl-Hexahydroapoerysopine
Fang, Da-Shu; Deng, Jun; Zheng, Jianfeng; Li, Wei-Dong Z.; Chemical Communications  (2022) –; doi:10.1039/D2CC01892F

data_7130063
_publ_section_title
;
 A Stereospecific Total Synthesis of dl-Hexahydroapoerysopine
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC01892F
_journal_year                    2022
_chemical_formula_moiety         'C18 H23 N O3'
_chemical_formula_sum            'C18 H23 N O3'
_chemical_formula_weight         301.37
_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     dual
_audit_creation_date             2021-09-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6403)
;
_audit_update_record
;
2021-10-14 deposited with the CCDC.	2022-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.669(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.8274(5)
_cell_length_b                   9.7027(4)
_cell_length_c                   12.2527(5)
_cell_measurement_reflns_used    2500
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5530
_cell_measurement_theta_min      4.0890
_cell_volume                     1523.32(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0892
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.857
_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    -47.00  22.00   1.00    3.63    --   18.58 -57.00   0.00   69
  2  \w      1.00  40.00   1.00    3.63    --   18.58  77.00-150.00   39
  3  \w    -50.00  40.00   1.00    3.63    --   18.58 -57.00-120.00   90
  4  \w    -18.00   9.00   1.00    3.63    --  -18.78 -77.00 -90.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0549723000
_diffrn_orient_matrix_UB_12      0.0068524000
_diffrn_orient_matrix_UB_13      0.0080884000
_diffrn_orient_matrix_UB_21      -0.0046184000
_diffrn_orient_matrix_UB_22      0.0720855000
_diffrn_orient_matrix_UB_23      -0.0082300000
_diffrn_orient_matrix_UB_31      -0.0059822000
_diffrn_orient_matrix_UB_32      0.0091958000
_diffrn_orient_matrix_UB_33      0.0567165000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0288
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6642
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.857
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.892
_diffrn_reflns_theta_min         3.622
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71901
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       block
_exptl_crystal_F_000             648
_exptl_crystal_size_max          0.32
_exptl_crystal_size_mid          0.31
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.177
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3436
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0815
_refine_ls_R_factor_gt           0.0551
_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^)+(0.0379P)^2^+0.6242P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1188
_refine_ls_wR_factor_ref         0.1365
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2333
_reflns_number_total             3436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc01892f2.cif
_cod_data_source_block           20210928-dengjun-fds-20210812
_cod_database_code               7130063
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C18 H23 N O3'
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.972
_reflns_odcompleteness_completeness 99.58
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C7(H7), C8(H8), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B), C10(H10A,H10B), C6(H6A,H6B), C4(H4A,H4B), C5(H5A,H5B), C2(H2A,H2B)
2.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C13(H13)
2.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C)
;
_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 1.456
_oxdiff_exptl_absorpt_empirical_full_min 0.639