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_1556635
_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         'C39 H39 N5 O5'
_chemical_formula_sum            'C39 H39 N5 O5'
_chemical_formula_weight         657.75
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-03-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-08-01 deposited with the CCDC.	2019-12-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 79.1361(11)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.80408(14)
_cell_length_b                   18.74504(18)
_cell_length_c                   31.2581(4)
_cell_measurement_reflns_used    13858
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.6640
_cell_measurement_theta_min      3.7250
_cell_volume                     6792.46(14)
_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    'SIR2004 (Burla et al., 2007)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_details
;
  1 omega  -74.00  -16.80   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  -19.0000   60.0000 143

  2 omega  -94.00  -62.80   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000   90.0000 78

  3 omega   24.00   50.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -60.0000 65

  4 omega    2.00   37.20   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   90.0000 88

  5 omega   -6.00   68.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -97.0000 -153.0000 185

  6 omega    0.00   26.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000   90.0000 65

  7 omega   50.00  103.20   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -90.0000 133

  8 omega  -16.00   52.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000   90.0000 170

  9 omega   61.00   93.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -150.0000 80

 10 omega   45.00   74.20   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   90.0000 73

 11 omega   46.00   72.00   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000   90.0000 65

 12 omega   60.00  103.20   0.4000   16.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   77.0000  -60.0000 108

 13 omega   74.00  100.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -97.0000 -153.0000 65

 14 omega  100.80  178.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -60.0000 193

 15 omega   46.00   85.20   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 98

 16 omega   38.00  113.20   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -60.0000 188

 17 omega   42.00  108.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   90.0000 165

 18 omega   83.00  175.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000 -120.0000 230

 19 omega   40.00   90.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 125

 20 omega   56.00   82.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  150.0000 65

 21 omega  111.00  169.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 145

 22 omega   45.00   73.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

 23 omega   68.00   94.00   0.4000   52.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 65
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1220333000
_diffrn_orient_matrix_UB_12      0.0177796000
_diffrn_orient_matrix_UB_13      -0.0076587000
_diffrn_orient_matrix_UB_21      0.0513503000
_diffrn_orient_matrix_UB_22      0.0252290000
_diffrn_orient_matrix_UB_23      -0.0465206000
_diffrn_orient_matrix_UB_31      -0.0115330000
_diffrn_orient_matrix_UB_32      -0.0761516000
_diffrn_orient_matrix_UB_33      -0.0172119000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            11515
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.096
_diffrn_reflns_theta_max         67.096
_diffrn_reflns_theta_min         3.722
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.697
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84160
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       plate
_exptl_crystal_F_000             2784
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.381
_refine_diff_density_min         -0.274
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     890
_refine_ls_number_reflns         11515
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0596
_refine_ls_R_factor_gt           0.0516
_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^)+(0.0903P)^2^+0.7126P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1400
_refine_ls_wR_factor_ref         0.1465
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9893
_reflns_number_total             11515
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04880d2.cif
_cod_data_source_block           201803150_tw
_cod_depositor_comments
;Adding full bibliography for 1556630--1556636.cif.

 Adding full bibliography for 1556630--1556636.cif.
;
_cod_original_cell_volume        6792.46(13)
_cod_database_code               1556635
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C40H30N3O5Br1
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 94.43
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6569(10)
 0.3431(10)
2. 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
3. Rigid bond restraints
 C36', C37'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C24, C25
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C36') \\sim Ueq, Uanis(C37') \\sim Ueq, Uanis(C38') \\sim Ueq,
Uanis(C39') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C33') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5.a Ternary CH refined with riding coordinates:
 C16(H16), C18(H18), C19(H19), C20(H20), C28(H28), C30(H30), C16'(H16'),
 C18'(H18'), C19'(H19'), C20'(H20'), C28'(H28'), C30'(H30')
5.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C21(H21A,H21B), C33(H33A,H33B), C2'(H2'A,H2'B),
 C4'(H4'A,H4'B), C21'(H21C,H21D), C33'(H33C,H33D)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C23(H23), C24(H24), C25(H25),
 C26(H26), C27(H27), C31(H31), C32(H32), C35(H35), C36(H36), C37(H37), C38(H38),
  C39(H39), C10'(H10'), C11'(H11'), C13'(H13'), C14'(H14'), C23'(H23'),
 C24'(H24'), C25'(H25'), C26'(H26'), C27'(H27'), C31'(H31'), C32'(H32'),
 C35'(H35'), C36'(H36'), C37'(H37'), C38'(H38'), C39'(H39')
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C7'(H7'A,H7'B,H7'C),
 C8'(H8'A,H8'B,H8'C), C15'(H15D,H15E,H15F)
;
_olex2_submission_special_instructions 'No special instructions were received'