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_4515662
_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         'C16 H26 F3 N O2'
_chemical_formula_sum            'C16 H26 F3 N O2'
_chemical_formula_weight         321.38
_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             2016-12-13
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.5790(3)
_cell_length_b                   16.9733(5)
_cell_length_c                   18.2465(4)
_cell_measurement_reflns_used    3912
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      63.14
_cell_measurement_theta_min      3.56
_cell_volume                     3586.05(16)
_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 0.995
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0810
_diffrn_reflns_av_unetI/netI     0.0662
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            23876
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.675
_diffrn_reflns_theta_min         3.556
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.832
_exptl_absorpt_correction_T_max  0.7535
_exptl_absorpt_correction_T_min  0.5957
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0736 before and 0.0642 after correction.
The Ratio of minimum to maximum transmission is 0.7906.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.191
_exptl_crystal_description       needle
_exptl_crystal_F_000             1376
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.326
_exptl_crystal_size_mid          0.105
_exptl_crystal_size_min          0.083
_refine_diff_density_max         0.211
_refine_diff_density_min         -0.160
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details
;
 Flack x determined using 1672 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     415
_refine_ls_number_reflns         6813
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.010
_refine_ls_R_factor_all          0.0831
_refine_ls_R_factor_gt           0.0515
_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^)+(0.0514P)^2^+0.0900P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1106
_refine_ls_wR_factor_ref         0.1265
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    0.984
_reflns_Friedel_fraction_max     0.953
_reflns_number_gt                4827
_reflns_number_total             6813
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b01253_si_005.cif
_cod_data_source_block           hx1216c
_cod_database_code               4515662
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.934
_shelx_estimated_absorpt_t_min   0.773
_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:
 C1A(H1AA), C3A(H3A), C1B(H1BA), C3B(H3B)
2.b Secondary CH2 refined with riding coordinates:
 C4A(H4AA,H4AB), C6A(H6AA,H6AB), C7A(H7AA,H7AB), C10A(H10A,H10B), C4B(H4BA,
 H4BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB), C10B(H10C,H10D)
2.c Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC), C14A(H14A,H14B,H14C), C15A(H15A,
 H15B,H15C), C16A(H16A,H16B,H16C), C8B(H8BA,H8BB,H8BC), C9B(H9BA,H9BB,H9BC),
 C14B(H14D,H14E,H14F), C15B(H15D,H15E,H15F), C16B(H16D,H16E,H16F)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id CZ-4
_olex2_submission_special_instructions 'No special instructions were received'