Iron(II)-Catalyzed Azidotrifluoromethylation of Olefins and N-Heterocycles for Expedient Vicinal Trifluoromethyl Amine Synthesis.
Zhu, Cheng-Liang; Wang, Cheng; Qin, Qi-Xue; Yruegas, Sam; Martin, Caleb D.; Xu, Hao; ACS catalysis 8 (2018) 5032–5037; doi:10.1021/acscatal.8b01253

data_4515660
_publ_section_title
;
 Iron(II)-Catalyzed Azidotrifluoromethylation of Olefins and
 N-Heterocycles for Expedient Vicinal Trifluoromethyl Amine Synthesis.
;
_journal_issue                   6
_journal_name_full               'ACS catalysis'
_journal_page_first              5032
_journal_page_last               5037
_journal_paper_doi               10.1021/acscatal.8b01253
_journal_volume                  8
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H21 F3 N2 O4 S, C H Cl3'
_chemical_formula_sum            'C18 H22 Cl3 F3 N2 O4 S'
_chemical_formula_weight         525.78
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2016-11-14
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.1287(3)
_cell_length_b                   17.2349(8)
_cell_length_c                   21.6302(11)
_cell_measurement_reflns_used    9970
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.23
_cell_measurement_theta_min      2.56
_cell_volume                     2284.74(19)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'COSMO (BRUKER, V1.61, 2009)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 8.36
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0241
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            11991
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.220
_diffrn_reflns_theta_min         3.279
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    4.968
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6362
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0762 before and 0.0577 after correction. The Ratio of minimum to maximum transmission is 0.8442. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_description       block
_exptl_crystal_F_000             1080
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.346
_exptl_crystal_size_mid          0.336
_exptl_crystal_size_min          0.258
_refine_diff_density_max         0.624
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 1722 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.031(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     287
_refine_ls_number_reflns         4343
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0386
_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^)+(0.0398P)^2^+2.0763P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0983
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.711
_reflns_Friedel_fraction_full    0.969
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                4213
_reflns_number_total             4343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01253_si_002.cif
_cod_data_source_block           hx1116a
_cod_database_code               4515660
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.360
_shelx_estimated_absorpt_t_min   0.278
_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 Ternary CH refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C6(H6A,H6B)
2.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C16(H16), C17(H17)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a glass fibre with paratone oil'
_olex2_submission_original_sample_id CZ-2
_olex2_submission_special_instructions 'No special instructions were received'