Regio- and diastereoselective dearomatizations of N-alkyl activated azaarenes: the maximization of the reactive sites
Miao, Hong-Jie; Wang, Le-Le; Han, Hua-Bin; Zhao, Yong-De; Wang, Qi-Lin; Bu, Zhan-Wei; Chemical Science 11 (2020) 1418–1424; doi:10.1039/C9SC04880D

data_1556634
_publ_section_title
;
 Regio- and diastereoselective dearomatizations of N-alkyl activated
 azaarenes: the maximization of the reactive sites
;
_journal_issue                   5
_journal_name_full               'Chemical Science'
_journal_page_first              1418
_journal_page_last               1424
_journal_paper_doi               10.1039/C9SC04880D
_journal_volume                  11
_journal_year                    2020
_chemical_formula_moiety         'C31 H31 Br N2 O'
_chemical_formula_sum            'C31 H31 Br N2 O'
_chemical_formula_weight         527.49
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2019-04-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-08-17 deposited with the CCDC.	2019-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.869(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4850(5)
_cell_length_b                   10.8239(5)
_cell_length_c                   16.4134(7)
_cell_measurement_reflns_used    3325
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.7610
_cell_measurement_theta_min      4.0450
_cell_volume                     2573.07(18)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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
;
  1 omega -101.00  -17.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -57.0000    0.0000 84

  2 omega -108.00  -75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000   30.0000 33

  3 omega   -3.00   22.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -180.0000 25

  4 omega   58.00   85.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -180.0000 27

  5 omega   18.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000   30.0000 40

  6 omega   45.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -150.0000 26

  7 omega  -31.00   21.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000  -60.0000 52

  8 omega    0.00   26.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -150.0000 26

  9 omega  -33.00   -7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000 -150.0000 26

 10 omega   13.00   59.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000 -150.0000 46

 11 omega  -31.00   -5.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -37.0000   30.0000 26

 12 omega    1.00   38.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   90.0000 37

 13 omega   52.00   77.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   90.0000 25

 14 omega   38.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -180.0000 33

 15 omega   58.00   87.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 29

 16 omega   60.00   91.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 31

 17 omega   41.00  106.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 65

 18 omega   42.00   97.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 55

 19 omega   67.00  113.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000 -180.0000 46

 20 omega   38.00   72.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 34

 21 omega   47.00   78.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -150.0000 31

 22 omega  134.00  175.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -150.0000 41

 23 omega  103.00  129.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000 -150.0000 26

 24 omega   57.00   99.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   30.0000 42

 25 omega   67.00  109.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   90.0000 42

 26 omega   87.00  174.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   30.0000  -90.0000 87
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0560458000
_diffrn_orient_matrix_UB_12      -0.0882394000
_diffrn_orient_matrix_UB_13      -0.0553746000
_diffrn_orient_matrix_UB_21      -0.0365383000
_diffrn_orient_matrix_UB_22      0.1112162000
_diffrn_orient_matrix_UB_23      -0.0494024000
_diffrn_orient_matrix_UB_31      0.0826638000
_diffrn_orient_matrix_UB_32      -0.0106723000
_diffrn_orient_matrix_UB_33      -0.0574768000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_unetI/netI     0.0441
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10451
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.055
_diffrn_reflns_theta_max         67.055
_diffrn_reflns_theta_min         4.040
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.372
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90797
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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    1.362
_exptl_crystal_description       prism
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.450
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         4590
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.015
_refine_ls_R_factor_all          0.0603
_refine_ls_R_factor_gt           0.0444
_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^)+(0.0616P)^2^+0.5371P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1123
_refine_ls_wR_factor_ref         0.1261
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3531
_reflns_number_total             4590
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04880d2.cif
_cod_data_source_block           20190484
_cod_depositor_comments
;Adding full bibliography for 1556630--1556636.cif.

 Adding full bibliography for 1556630--1556636.cif.
;
_cod_database_code               1556634
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4Br1
_shelx_estimated_absorpt_t_max   0.797
_shelx_estimated_absorpt_t_min   0.689
_reflns_odcompleteness_completeness 99.96
_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:
 C7(H7), C8(H8), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C20(H20A,H20B), C22(H22A,H22B)
2.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C26(H26), C27(H27), C29(H29), C30(H30)
2.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C31(H31A,H31B,H31C)
;
_olex2_submission_special_instructions 'No special instructions were received'