Copper-catalyzed regioselective cyclization of vinyl azides by gem-difluoromethylene for trisubstituted pyridines
Liu, Zhenhua; Zhu, Guangyu; Gao, Wen; Yang, Lin; Ji, Huimin; Tong, Lili; Tang, Bo; Organic Chemistry Frontiers 6 (2019) 468–; doi:10.1039/C8QO01212A

data_1554536
_publ_section_title
;
 Copper-catalyzed regioselective cyclization of vinyl azides by
 gem-difluoromethylene for trisubstituted pyridines
;
_journal_issue                   4
_journal_name_full               'Organic Chemistry Frontiers'
_journal_page_first              468
_journal_paper_doi               10.1039/C8QO01212A
_journal_volume                  6
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C20 H15 Br2 N O2'
_chemical_formula_sum            'C20 H15 Br2 N O2'
_chemical_formula_weight         461.15
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-03-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-06-30 deposited with the CCDC.
2018-12-21 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   7.0667(3)
_cell_length_b                   23.0878(10)
_cell_length_c                   21.9663(7)
_cell_measurement_reflns_used    2999
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      70.9110
_cell_measurement_theta_min      5.5590
_cell_volume                     3583.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XH (Sheldrick, 2008)'
_computing_structure_solution    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0793
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     55.00 121.00   1.00    1.00    --   54.00  57.00 -60.00   66
  2  \w     73.00 100.00   1.00    1.00    --   54.00  57.00 -30.00   27
  3  \w    125.00 152.00   1.00    1.00    --  108.00 111.00 -60.00   27
  4  \w     96.00 164.00   1.00    1.00    --  108.00  63.00 -90.00   68
  5  \w     80.00 113.00   1.00    1.00    --   54.00 156.00   0.00   33
  6  \w    133.00 178.00   1.00    1.00    --  108.00  37.00 120.00   45
  7  \w     36.00 113.00   1.00    1.00    --  108.00-111.00  90.00   77
  8  \w     24.00 104.00   1.00    1.00    --   54.00-125.00  90.00   80
  9  \w     38.00 112.00   1.00    1.00    --  108.00 -50.00-150.00   74
 10  \w     19.00  47.00   1.00    1.00    --    0.00  57.00-180.00   28
 11  \w    -14.00  16.00   1.00    1.00    --    0.00  57.00-180.00   30
 12  \w    -50.00 -23.00   1.00    1.00    --    0.00 156.00   0.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0620804000
_diffrn_orient_matrix_UB_12      0.0102703000
_diffrn_orient_matrix_UB_13      -0.0663586000
_diffrn_orient_matrix_UB_21      -0.1258303000
_diffrn_orient_matrix_UB_22      0.0507311000
_diffrn_orient_matrix_UB_23      0.0208240000
_diffrn_orient_matrix_UB_31      0.1670704000
_diffrn_orient_matrix_UB_32      0.0420401000
_diffrn_orient_matrix_UB_33      -0.0089863000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_unetI/netI     0.0507
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            7839
_diffrn_reflns_theta_full        67.07
_diffrn_reflns_theta_max         67.07
_diffrn_reflns_theta_min         3.83
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.846
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32797
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_density_diffrn    1.709
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1824
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.871
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.103
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.00
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         5011
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0415
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0637P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1129
_reflns_number_gt                4510
_reflns_number_total             5011
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c8qo01212a2.cif
_cod_data_source_block           11
_cod_database_code               1554536
_reflns_odcompleteness_completeness 99.86
_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.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C31(H31A,H31B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C8(H8), C13(H13), C16(H16), C17(H17),
 C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C28(H28), C33(H33),
  C36(H36), C37(H37), C39(H39), C40(H40)
2.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C32(H32A,H32B,H32C)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.944
_oxdiff_exptl_absorpt_empirical_full_min 0.533