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_4518522
_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_formula_moiety         'C20 H19 N O3'
_chemical_formula_sum            'C20 H19 N O3'
_chemical_formula_weight         321.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.5023(7)
_cell_length_b                   7.8493(3)
_cell_length_c                   22.7256(7)
_cell_measurement_reflns_used    4153
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.0740
_cell_measurement_theta_min      3.8420
_cell_volume                     3300.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.68a (Rigaku OD, 2019)'
_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_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     34.00 105.00   1.00    3.50    --  106.49 -77.00  30.00   71
  2  \w     38.00 105.00   1.00    3.50    --  106.49 -77.00  90.00   67
  3  \w     52.00 111.00   1.00    3.50    --  106.49-127.00 -73.00   59
  4  \w     38.00  97.00   1.00    3.50    --  106.49 -77.00-180.00   59
  5  \w    101.00 174.00   1.00    3.50    --  106.49  19.00 -90.00   73
  6  \w    110.00 178.00   1.00    3.50    --  106.49  94.00 -71.00   68
  7  \w    -26.00  27.00   1.00    0.50    --   48.45 -19.00-180.00   53
  8  \w   -156.00 -75.00   1.00    3.50    --  -86.25 -29.00 -17.00   81
  9  \w   -120.00 -36.00   1.00    0.50    --  -48.45 -29.00 -17.00   84
 10  \w    -43.00 -14.00   1.00    3.50    --  -86.25  38.00 -30.00   29
 11  \w    -85.00 -36.00   1.00    3.50    --  -86.25 127.00   2.00   49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0459585000
_diffrn_orient_matrix_UB_12      -0.0358734000
_diffrn_orient_matrix_UB_13      0.0551135000
_diffrn_orient_matrix_UB_21      0.0621102000
_diffrn_orient_matrix_UB_22      -0.0650244000
_diffrn_orient_matrix_UB_23      -0.0392200000
_diffrn_orient_matrix_UB_31      0.0312521000
_diffrn_orient_matrix_UB_32      0.1817553000
_diffrn_orient_matrix_UB_33      -0.0030804000
_diffrn_radiation_collimation    0.3
_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  0.0948
_diffrn_reflns_av_unetI/netI     0.0811
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            15563
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.067
_diffrn_reflns_theta_max         67.067
_diffrn_reflns_theta_min         3.890
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.702
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.34188
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.68a (Rigaku Oxford Diffraction, 2019)
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    1.293
_exptl_crystal_description       block
_exptl_crystal_F_000             1360
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.193
_refine_diff_density_min         -0.190
_refine_diff_density_rms         0.045
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0695
_refine_ls_R_factor_gt           0.0565
_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^)+(0.0845P)^2^+0.4974P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1526
_refine_ls_wR_factor_ref         0.1650
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2275
_reflns_number_total             2931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c05515_si_002.cif
_cod_data_source_block           200711b
_cod_original_cell_volume        3300.45(19)
_cod_database_code               4518522
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CNO
_shelx_estimated_absorpt_t_max   0.986
_shelx_estimated_absorpt_t_min   0.979
_reflns_odcompleteness_completeness 99.29
_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.a Ternary CH refined with riding coordinates:
 C2(H2)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C14(H14A,H14B)
2.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C17(H17),
 C18(H18)
2.d X=CH2 refined with riding coordinates:
 C20(H20A,H20B)
2.e Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C)
;
_shelx_res_checksum              6666
_shelx_hkl_checksum              26397
_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 2.590
_oxdiff_exptl_absorpt_empirical_full_min 0.223