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_1556633
_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         'C28 H29 N3 O'
_chemical_formula_sum            'C28 H29 N3 O'
_chemical_formula_weight         423.54
_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             2018-10-28
_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                 102.053(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.0448(4)
_cell_length_b                   14.0503(6)
_cell_length_c                   18.8685(6)
_cell_measurement_reflns_used    2345
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8790
_cell_measurement_theta_min      3.9340
_cell_volume                     2344.99(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    '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  -46.00    8.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   37.0000  -60.0000 54

  2 omega  -41.00  -13.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   77.0000    0.0000 28

  3 omega   10.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   77.0000    0.0000 26

  4 omega   38.00   96.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   37.0000  -30.0000 58

  5 omega    9.00   67.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000   60.0000 58

  6 omega  -30.00    2.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  -90.0000 32

  7 omega   32.00   64.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -180.0000 32

  8 omega   78.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -180.0000 30

  9 omega   14.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -77.0000  -90.0000 49

 10 omega   71.00  103.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000 -180.0000 32

 11 omega   57.00   82.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -30.0000 25

 12 omega   58.00   87.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000 -120.0000 29

 13 omega   42.00   83.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   90.0000 41

 14 omega  103.00  173.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   60.0000 70

 15 omega   90.00  177.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 87

 16 omega   38.00   89.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 51

 17 omega  134.00  175.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 41

 18 omega   91.00  130.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000  120.0000 39

 19 omega   42.00   98.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000   30.0000 56

 20 omega   74.00  109.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 35

 21 omega   60.00   86.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  -30.0000 26

 22 omega   45.00  132.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000   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      -0.0012261000
_diffrn_orient_matrix_UB_12      0.0977823000
_diffrn_orient_matrix_UB_13      -0.0370444000
_diffrn_orient_matrix_UB_21      0.0409898000
_diffrn_orient_matrix_UB_22      0.0483960000
_diffrn_orient_matrix_UB_23      0.0748410000
_diffrn_orient_matrix_UB_31      0.1692540000
_diffrn_orient_matrix_UB_32      -0.0109986000
_diffrn_orient_matrix_UB_33      -0.0004882000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0370
_diffrn_reflns_av_unetI/netI     0.0425
_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       -6
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            9364
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.065
_diffrn_reflns_theta_max         67.065
_diffrn_reflns_theta_min         3.954
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.573
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.200
_exptl_crystal_description       prism
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.200
_refine_diff_density_min         -0.134
_refine_diff_density_rms         0.033
_refine_ls_extinction_coef       0.0016(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     293
_refine_ls_number_reflns         4187
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0727
_refine_ls_R_factor_gt           0.0527
_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^)+(0.0749P)^2^+0.1694P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1432
_refine_ls_wR_factor_ref         0.1669
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2936
_reflns_number_total             4187
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04880d2.cif
_cod_data_source_block           201810620
_cod_depositor_comments
;Adding full bibliography for 1556630--1556636.cif.

 Adding full bibliography for 1556630--1556636.cif.
;
_cod_original_cell_volume        2344.99(18)
_cod_database_code               1556633
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3N2
_shelx_estimated_absorpt_t_max   0.929
_shelx_estimated_absorpt_t_min   0.879
_reflns_odcompleteness_completeness 99.93
_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. Rigid bond restraints
 C27, C26
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C17(H17), C21(H21)
4.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C20(H20A,H20B), C22(H22A,H22B)
4.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C13(H13), C14(H14), C19(H19), C24(H24), C25(H25),
 C26(H26), C27(H27), C28(H28)
4.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C)
;
_olex2_submission_special_instructions 'No special instructions were received'