Dual C-H functionalization of N-aryl tetrahydroisoquinolines: a highly diastereoselective synthesis of dibenzo[a,f]quinolizines via visible-light induced oxidation and inverse electron-demand aza-Diels-Alder reaction.
Xu, Guo-Qiang; Li, Chen-Guang; Liu, Ming-Qian; Cao, Jian; Luo, Yong-Chun; Xu, Peng-Fei; Chemical communications (Cambridge, England) 52 (2016) 1190–1193; doi:10.1039/c5cc08833j

data_7118353
_publ_section_title
;
 Dual C-H functionalization of N-aryl tetrahydroisoquinolines: a highly
 diastereoselective synthesis of dibenzo[a,f]quinolizines via
 visible-light induced oxidation and inverse electron-demand
 aza-Diels-Alder reaction.
;
_journal_issue                   6
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1190
_journal_page_last               1193
_journal_paper_doi               10.1039/c5cc08833j
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C20 H18 Br N2 O2'
_chemical_formula_sum            'C20 H18 Br N2 O2'
_chemical_formula_weight         398.27
_chemical_melting_point          333
_chemical_name_systematic
;
 ? 
;
_chemical_properties_physical    Oxygen-sensitive
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2014.11.28 svn.r3106 for OlexSys, GUI svn.r4959)
;
_audit_update_record
;
2015-07-27 deposited with the CCDC.
2015-11-12 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.830(8)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   11.3148(10)
_cell_length_b                   7.1192(5)
_cell_length_c                   21.3182(15)
_cell_measurement_reflns_used    684
_cell_measurement_temperature    293.18(10)
_cell_measurement_theta_max      18.0780
_cell_measurement_theta_min      3.8260
_cell_volume                     1713.4(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.18(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega  -52.00   65.00   1.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -19.0000   60.0000 78

  2 omega   45.00   96.00   1.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854 -178.0000   60.0000 34

  3 omega   67.00   94.00   1.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000  150.0000 18

  4 omega   40.00   67.00   1.5000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  178.0000  120.0000 18
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0606601000
_diffrn_orient_matrix_UB_12      -0.0185588000
_diffrn_orient_matrix_UB_13      0.0082940000
_diffrn_orient_matrix_UB_21      -0.0021524000
_diffrn_orient_matrix_UB_22      -0.0782666000
_diffrn_orient_matrix_UB_23      -0.0205969000
_diffrn_orient_matrix_UB_31      0.0162995000
_diffrn_orient_matrix_UB_32      0.0587505000
_diffrn_orient_matrix_UB_33      -0.0248781000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0659
_diffrn_reflns_av_unetI/netI     0.1382
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            6448
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.38
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.415
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63035
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.544
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             812
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/n-hexane'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.063
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     226
_refine_ls_number_reflns         3375
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.2026
_refine_ls_R_factor_gt           0.0716
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0379P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1642
_reflns_number_gt                1325
_reflns_number_total             3375
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c5cc08833j2.cif
_cod_data_source_block           xugq0518
_cod_database_code               7118353
_reflns_odcompleteness_completeness 99.66
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C11(H11), C12(H12), C13(H13), C14(H14), C19(H19)
;
_olex2_date_sample_data_collection 2015-05-18
_olex2_submission_special_instructions 'No special instructions were received'