Copper-catalyzed difluoromethylation of propargylamide-substituted indoles: synthesis of mono- and bis-difluoromethylated indoloazepinone derivatives.
Hua, Hui-Liang; Zhang, Bo-Sheng; He, Yu-Tao; Qiu, Yi-Feng; Hu, Jing-Yuan; Yang, Yu-Chen; Liang, Yong-Min; Chemical communications (Cambridge, England) 52 (2016) 10396–10399; doi:10.1039/c6cc05745d

data_7124937
_publ_section_title
;
 Copper-catalyzed difluoromethylation of propargylamide-substituted
 indoles: synthesis of mono- and bis-difluoromethylated indoloazepinone
 derivatives.
;
_journal_issue                   68
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              10396
_journal_page_last               10399
_journal_paper_doi               10.1039/c6cc05745d
_journal_volume                  52
_journal_year                    2016
_chemical_formula_moiety         'C29 H28 F4 N2 O5'
_chemical_formula_sum            'C29 H28 F4 N2 O5'
_chemical_formula_weight         560.53
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-03-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2016-06-14 deposited with the CCDC.
2016-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 100.263(4)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   12.4966(6)
_cell_length_b                   9.7777(4)
_cell_length_c                   22.6334(12)
_cell_measurement_reflns_used    1938
_cell_measurement_temperature    290.83(10)
_cell_measurement_theta_max      22.7930
_cell_measurement_theta_min      3.7370
_cell_volume                     2721.3(2)
_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_environment      air
_diffrn_ambient_temperature      290.83(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  -34.00   31.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -38.0000   30.0000 65

  2 omega  -41.00   65.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854  -19.0000 -120.0000 106

  3 omega   37.00   63.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854 -178.0000   90.0000 26

  4 omega   50.00   81.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       20.5854 -178.0000 -150.0000 31
;
_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      0.0075893000
_diffrn_orient_matrix_UB_12      0.0130062000
_diffrn_orient_matrix_UB_13      0.0313091000
_diffrn_orient_matrix_UB_21      -0.0364329000
_diffrn_orient_matrix_UB_22      0.0560917000
_diffrn_orient_matrix_UB_23      -0.0053835000
_diffrn_orient_matrix_UB_31      -0.0440698000
_diffrn_orient_matrix_UB_32      -0.0440969000
_diffrn_orient_matrix_UB_33      0.0023952000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0558
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            10898
_diffrn_reflns_theta_full        26.02
_diffrn_reflns_theta_max         26.02
_diffrn_reflns_theta_min         3.31
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.112
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80986
_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            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1168
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.241
_refine_diff_density_min         -0.180
_refine_diff_density_rms         0.043
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         5349
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.1050
_refine_ls_R_factor_gt           0.0573
_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^)+(0.0534P)^2^+1.0598P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1308
_refine_ls_wR_factor_ref         0.1605
_reflns_number_gt                3083
_reflns_number_total             5349
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6cc05745d2.cif
_cod_data_source_block           huahl_0328_1
_cod_database_code               7124937
_reflns_odcompleteness_completeness 99.71
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C16(H16A,H16B), C28(H28A,H28B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C19(H19), C20(H20), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C)
;
_olex2_date_sample_data_collection 2016-03-28
_olex2_submission_special_instructions 'No special instructions were received'