Highly Diastereo- and Enantioselective Synthesis of Tetrahydrobenzo[b]azocines via Palladium-Catalyzed [4 + 4] Cycloaddition
Gao, Can; Wang, Xunhua; Liu, Jitian; Li, Xiaoxun; ACS Catalysis  (2021) 2684–2690; doi:10.1021/acscatal.0c05515

data_4518523
_publ_section_title
;
 Highly Diastereo- and Enantioselective Synthesis of
 Tetrahydrobenzo[b]azocines via Palladium-Catalyzed [4 + 4] Cycloaddition
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              2684
_journal_page_last               2690
_journal_paper_doi               10.1021/acscatal.0c05515
_journal_year                    2021
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C20 H17 Br4 N O3'
_chemical_formula_sum            'C20 H17 Br4 N O3'
_chemical_formula_weight         638.98
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-10-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_cell_angle_alpha                90
_cell_angle_beta                 104.756(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.1259(9)
_cell_length_b                   7.5367(3)
_cell_length_c                   20.6213(5)
_cell_measurement_reflns_used    7606
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      75.9110
_cell_measurement_theta_min      3.2180
_cell_volume                     4227.1(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_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    100.00 178.00   1.00    1.20    --  106.49  38.00   0.00   78
  2  \w     94.00 178.00   1.00    1.20    --  106.49  19.00 -30.00   84
  3  \w     54.00  79.00   1.00    0.27    --   48.45  39.00 -99.00   25
  4  \w    100.00 137.00   1.00    1.20    --  106.49  39.00 -99.00   37
  5  \w     94.00 178.00   1.00    1.20    --  106.49  19.00-120.00   84
  6  \w     37.00 105.00   1.00    1.20    --  106.49 -77.00 -30.00   68
  7  \w     34.00  65.00   1.00    1.20    --  106.49 -57.00   0.00   31
  8  \w     34.00  66.00   1.00    1.20    --  106.49 -57.00  30.00   32
  9  \w     34.00  66.00   1.00    1.20    --  106.49 -57.00 150.00   32
 10  \w    -24.00  43.00   1.00    0.27    --   48.45 -39.00 105.00   67
 11  \w    -42.00  25.00   1.00    0.27    --  -48.45  38.00 -30.00   67
 12  \w    -43.00  24.00   1.00    0.27    --  -48.45  39.00 -99.00   67
 13  \w    -44.00 -19.00   1.00    1.20    --  -86.25  39.00 -99.00   25
 14  \w    -63.00 -14.00   1.00    1.20    --  -86.25  57.00  60.00   49
 15  \w   -120.00 -36.00   1.00    0.27    --  -48.45 -39.00 105.00   84
 16  \w   -140.00-115.00   1.00    1.20    --  -86.25 -39.00 105.00   25
 17  \w   -152.00 -73.00   1.00    1.20    --  -86.25 -38.00 120.00   79
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0032017000
_diffrn_orient_matrix_UB_12      -0.1002935000
_diffrn_orient_matrix_UB_13      -0.0660763000
_diffrn_orient_matrix_UB_21      0.0565823000
_diffrn_orient_matrix_UB_22      -0.0055216000
_diffrn_orient_matrix_UB_23      0.0160178000
_diffrn_orient_matrix_UB_31      0.0000133000
_diffrn_orient_matrix_UB_32      -0.1779502000
_diffrn_orient_matrix_UB_33      0.0366712000
_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  0.0352
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            12929
_diffrn_reflns_point_group_measured_fraction_full 0.794
_diffrn_reflns_point_group_measured_fraction_max 0.794
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.250
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.481
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58197
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    2.008
_exptl_crystal_description       block
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.660
_refine_diff_density_min         -0.411
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1811 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.022(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     507
_refine_ls_number_reflns         5994
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0276
_refine_ls_R_factor_gt           0.0258
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0287P)^2^+1.5597P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0634
_refine_ls_wR_factor_ref         0.0642
_reflns_Friedel_coverage         0.487
_reflns_Friedel_fraction_full    0.567
_reflns_Friedel_fraction_max     0.567
_reflns_number_gt                5702
_reflns_number_total             5994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c05515_si_003.cif
_cod_data_source_block           201009c
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_moiety     '2(C20 H17 Br4 N O3)'
_cod_original_formula_sum        'C40 H34 Br8 N2 O6'
_cod_original_formula_units_Z    4
_cod_original_formula_weight     1277.97
_cod_database_code               4518523
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CNO
_shelx_estimated_absorpt_t_max   0.833
_shelx_estimated_absorpt_t_min   0.764
_reflns_odcompleteness_completeness 98.63
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C13(H13), C5(H5)
2.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C28(H28A,H28B), C29(H29A,H29B), C19(H19A,H19B), C33(H33A,
 H33B), C37(H37A,H37B)
2.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C14(H14), C25(H25), C27(H27), C35(H35), C36(H36), C40(H40), N2(H2),
 C18(H18), C24(H24), C26(H26), C30(H30), C31(H31), C34(H34)
2.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C)
;
_shelx_res_checksum              98821
_shelx_hkl_checksum              6730
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.724