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_1556632
_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         'C46 H42 Br N3 O'
_chemical_formula_sum            'C46 H42 Br N3 O'
_chemical_formula_weight         732.73
_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     iterative
_audit_creation_date             2018-10-26
_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                 94.804(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.2078(3)
_cell_length_b                   19.1520(5)
_cell_length_c                   18.9514(4)
_cell_measurement_reflns_used    4592
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8150
_cell_measurement_theta_min      4.6030
_cell_volume                     3691.98(17)
_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
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_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  -43.00   20.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000  150.0000 63

  2 omega -103.00  -30.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -77.0000 -150.0000 73

  3 omega  -57.00  -32.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000 -180.0000 25

  4 omega -108.00  -76.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000 -180.0000 32

  5 omega   58.00  109.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -90.0000 51

  6 omega   -1.00   81.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000   30.0000 82

  7 omega    8.00   45.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000    0.0000 37

  8 omega    1.00   39.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  -60.0000 38

  9 omega    2.00   49.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000 -120.0000 47

 10 omega   76.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000    0.0000 25

 11 omega   75.00  105.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  150.0000 30

 12 omega   46.00   77.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000  -60.0000 31

 13 omega   40.00   84.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000   90.0000 44

 14 omega   57.00  105.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 48

 15 omega   50.00   76.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 26

 16 omega  124.00  157.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000 -180.0000 33

 17 omega   45.00   92.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   60.0000 47

 18 omega   58.00   91.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 33

 19 omega   44.00   89.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 45

 20 omega   44.00   98.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -120.0000 54

 21 omega   38.00   98.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 60

 22 omega  111.00  169.00   1.0000    7.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  -90.0000 58
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1391169000
_diffrn_orient_matrix_UB_12      -0.0170584000
_diffrn_orient_matrix_UB_13      -0.0208177000
_diffrn_orient_matrix_UB_21      0.0501147000
_diffrn_orient_matrix_UB_22      -0.0040021000
_diffrn_orient_matrix_UB_23      0.0788750000
_diffrn_orient_matrix_UB_31      -0.0326649000
_diffrn_orient_matrix_UB_32      -0.0785198000
_diffrn_orient_matrix_UB_33      0.0005240000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0612
_diffrn_reflns_av_unetI/netI     0.0582
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            14208
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         4.618
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.819
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.318
_exptl_crystal_description       prism
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.014
_refine_diff_density_min         -0.541
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     473
_refine_ls_number_reflns         6586
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0870
_refine_ls_R_factor_gt           0.0701
_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^)+(0.1123P)^2^+2.5906P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1909
_refine_ls_wR_factor_ref         0.2129
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5036
_reflns_number_total             6586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04880d2.cif
_cod_data_source_block           201810415
_cod_depositor_comments
;Adding full bibliography for 1556630--1556636.cif.

 Adding full bibliography for 1556630--1556636.cif.
;
_cod_original_cell_volume        3691.96(16)
_cod_database_code               1556632
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2Br1
_shelx_estimated_absorpt_t_max   0.839
_shelx_estimated_absorpt_t_min   0.735
_reflns_odcompleteness_completeness 99.94
_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. Uiso/Uaniso restraints and constraints
Uanis(C45A) \\sim Ueq, Uanis(C44A) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45)
\\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C43A) \\sim Ueq,
Uanis(C42A) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C41A) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C46A) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C40) = Uanis(C40A)
Uanis(C41) = Uanis(C41A)
Uanis(C46) = Uanis(C46A)
Uanis(C45) = Uanis(C45A)
Uanis(C44) = Uanis(C44A)
Uanis(C43) = Uanis(C43A)
Uanis(C42) = Uanis(C42A)
3. Others
 Sof(C40A)=Sof(H40C)=Sof(H40D)=1-FVAR(1)
 Sof(C40)=Sof(H40A)=Sof(H40B)=FVAR(1)
 Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(H44A)=
 Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=1-FVAR(2)
 Sof(C41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=
 Sof(H45)=Sof(C46)=Sof(H46)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C15(H15), C22(H22), C23(H23), C31(H31)
4.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C12(H12A,H12B), C24(H24A,H24B), C40(H40A,H40B), C40A(H40C,H40D)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C17(H17), C18(H18), C19(H19), C20(H20),
 C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C33(H33), C34(H34), C35(H35),
  C36(H36), C38(H38), C39(H39), C42A(H42A), C43A(H43A), C44A(H44A), C45A(H45A),
 C46A(H46A), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46)
4.d Fitted hexagon refined as free rotating group:
 C41A(C42A,C43A,C44A,C45A,C46A)
4.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_olex2_submission_special_instructions 'No special instructions were received'