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_1556636
_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         'C45 H39 Cl2 N3 O'
_chemical_formula_sum            'C45 H39 Cl2 N3 O'
_chemical_formula_weight         708.69
_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             2018-09-11
_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                 102.8973(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.58053(11)
_cell_length_b                   20.7753(2)
_cell_length_c                   29.2921(3)
_cell_measurement_reflns_used    11310
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.8680
_cell_measurement_theta_min      3.9470
_cell_volume                     8055.96(13)
_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  -86.00  -33.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000 -180.0000 106

  2 omega  -92.00  -66.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  -30.0000 52

  3 omega  -24.00   35.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000   57.0000 -180.0000 118

  4 omega  -87.00  -34.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -      -33.5000  178.0000  -60.0000 106

  5 omega   -1.00  109.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   19.0000 -150.0000 220

  6 omega  -14.00   34.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -57.0000   60.0000 96

  7 omega   77.00  103.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000   90.0000 52

  8 omega   59.00   93.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000    0.0000 68

  9 omega   23.00   71.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -90.0000 96

 10 omega   58.00  101.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  150.0000 86

 11 omega   82.00  109.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  120.0000 54

 12 omega   39.00   67.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  -99.0000    0.0000 56

 13 omega   74.00  110.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734  178.0000  -30.0000 72

 14 omega   77.00  104.00   0.5000    4.5000
omega____ theta____ kappa____ phi______ frames
    -       36.4734   57.0000  -90.0000 54

 15 omega   97.00  156.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  150.0000 118

 16 omega   39.00   98.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  -60.0000 118

 17 omega   65.00  108.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000   30.0000 86

 18 omega  117.00  157.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000   90.0000 80

 19 omega   42.00   80.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  120.0000 76

 20 omega   53.00   79.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000 -180.0000 52

 21 omega   94.00  160.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   90.0000 132

 22 omega   41.00   99.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 116

 23 omega   74.00  164.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   60.0000 180

 24 omega   37.00  109.00   0.5000   27.5000
omega____ theta____ kappa____ phi______ frames
    -      108.0000 -111.0000  -30.0000 144
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0564917000
_diffrn_orient_matrix_UB_12      -0.0647875000
_diffrn_orient_matrix_UB_13      0.0041741000
_diffrn_orient_matrix_UB_21      -0.0773419000
_diffrn_orient_matrix_UB_22      -0.0255756000
_diffrn_orient_matrix_UB_23      -0.0428702000
_diffrn_orient_matrix_UB_31      0.0661083000
_diffrn_orient_matrix_UB_32      0.0254026000
_diffrn_orient_matrix_UB_33      -0.0325096000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0322
_diffrn_reflns_av_unetI/netI     0.0341
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            37627
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.075
_diffrn_reflns_theta_max         67.075
_diffrn_reflns_theta_min         3.352
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.725
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80582
_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_density_diffrn    1.169
_exptl_crystal_F_000             2976
_refine_diff_density_max         3.290
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.431
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     929
_refine_ls_number_reflns         14381
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.431
_refine_ls_R_factor_all          0.1448
_refine_ls_R_factor_gt           0.1225
_refine_ls_shift/su_max          0.546
_refine_ls_shift/su_mean         0.010
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3481
_refine_ls_wR_factor_ref         0.3780
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10018
_reflns_number_total             14381
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc04880d2.cif
_cod_data_source_block           201809362
_cod_depositor_comments
;Adding full bibliography for 1556630--1556636.cif.

 Adding full bibliography for 1556630--1556636.cif.
;
_cod_database_code               1556636
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C15H15O3
_reflns_odcompleteness_completeness 99.95
_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, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C36) = Uanis(C36A)
Uanis(C36') = Uanis(C1A)
3. Others
 Sof(H35C)=Sof(H35D)=Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(H37C)=Sof(H37D)=1-FVAR(1)
 Sof(H35A)=Sof(H35B)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H37A)=Sof(H37B)=FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H35G)=Sof(H35H)=Sof(H37G)=Sof(H37H)=1-FVAR(2)
 Sof(H35E)=Sof(H35F)=Sof(C36')=Sof(H36E)=Sof(H36F)=Sof(H37E)=Sof(H37F)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C25(H25), C7'(H7'), C8'(H8'), C9'(H9'), C25'(H25')
4.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C26(H26A,H26B), C35(H35A,H35B), C35(H35C,H35D), C36(H36A,
 H36B), C36A(H36C,H36D), C37(H37A,H37B), C37(H37C,H37D), C1A(H1AA,H1AB),
 C10'(H10C,H10D), C26'(H26C,H26D), C35'(H35E,H35F), C35'(H35G,H35H), C36'(H36E,
 H36F), C37'(H37E,H37F), C37'(H37G,H37H)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C18(H18), C19(H19), C21(H21), C23(H23), C24(H24), C28(H28), C29(H29), C30(H30),
  C31(H31), C32(H32), C40(H40), C41(H41), C43(H43), C44(H44), C2'(H2'),
 C3'(H3'), C5'(H5'), C12'(H12'), C13'(H13'), C14'(H14'), C15'(H15'), C16'(H16'),
  C18'(H18'), C19'(H19'), C21'(H21'), C23'(H23'), C24'(H24'), C28'(H28'),
 C29'(H29'), C30'(H30'), C31'(H31'), C32'(H32'), C40'(H40'), C41'(H41'),
 C43'(H43'), C44'(H44')
4.d Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C45'(H45D,H45E,H45F)
;
_olex2_submission_special_instructions 'No special instructions were received'