Direct Amine-Catalyzed Enantioselective Synthesis of Pentacyclic Dibenzo[<i>b</i>,<i>f</i>][1,4]oxazepine/Thiazepine-Fused Isoquinuclidines along with DFT Calculations.
Yadav, Jyothi; Pawar, Amol Prakash; Nagare, Yadav Kacharu; Iype, Eldhose; Rangan, Krishnan; Ohshita, Joji; Kumar, Dalip; Kumar, Indresh; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c02141

data_4038878
_publ_section_title
;
 Direct Amine-Catalyzed Enantioselective Synthesis of Pentacyclic
 Dibenzo[<i>b</i>,<i>f</i>][1,4]oxazepine/Thiazepine-Fused
 Isoquinuclidines along with DFT Calculations.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c02141
_journal_year                    2020
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C20 H18 Br N O2'
_chemical_formula_sum            'C20 H18 Br N O2'
_chemical_formula_weight         384.26
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4266(3)
_cell_length_b                   15.5268(6)
_cell_length_c                   16.3329(6)
_cell_measurement_reflns_used    7370
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      29.6840
_cell_measurement_theta_min      3.6190
_cell_volume                     1629.77(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.20a (Rigaku OD, 2015)'
_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_temperature      93(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.932
_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    -75.00 -33.00   0.50   41.42    --    0.00 -19.00  90.00   84
  2  \w    -22.00  58.00   0.50   41.42    --    0.00  57.00-180.00  160
  3  \w     48.00  88.00   0.50   41.42    --    0.00  57.00  30.00   80
  4  \w    -20.00  85.00   0.50   41.42    --    0.00  19.00  30.00  210
  5  \w    -48.00 -23.00   0.50   41.42    --    0.00 -57.00-150.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Pro: Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0298712000
_diffrn_orient_matrix_UB_12      0.0333723000
_diffrn_orient_matrix_UB_13      0.0271699000
_diffrn_orient_matrix_UB_21      0.0920930000
_diffrn_orient_matrix_UB_22      -0.0229724000
_diffrn_orient_matrix_UB_23      0.0098328000
_diffrn_orient_matrix_UB_31      0.0530190000
_diffrn_orient_matrix_UB_32      0.0210804000
_diffrn_orient_matrix_UB_33      -0.0324279000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            18037
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.909
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.777
_diffrn_reflns_theta_min         3.407
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.534
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68734
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    1.566
_exptl_crystal_description       Rod
_exptl_crystal_F_000             784
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.355
_refine_diff_density_min         -0.366
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 1522 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.009(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         4227
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0298P)^2^+0.5722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0598
_refine_ls_wR_factor_ref         0.0615
_reflns_Friedel_coverage         0.703
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.877
_reflns_number_gt                3897
_reflns_number_total             4227
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c02141_si_003.cif
_cod_data_source_block           exp_280-ap-i
_cod_database_code               4038878
_shelx_shelxl_version_number     2016/4
_reflns_odcompleteness_completeness 99.64
_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:
 C17(H17), C16(H16), C13(H13)
2.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C19(H19A,H19B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C2(H2), C11(H11), C8(H8), C10(H10)
2.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_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 1.367
_oxdiff_exptl_absorpt_empirical_full_min 0.861