Enantioselective Synthesis of Fluoroalkyl-Substituted syn-Diamines by the Asymmetric gem-Difunctionalization of 2,2,2-Trifluorodiazoethane
Li, Jiuling; Zhang, Dan; Chen, Jianghui; Ma, Chaoqun; Hu, Wenhao; ACS Catalysis  (2020) 4559–4565; doi:10.1021/acscatal.0c00972

data_4517527
_publ_section_title
;
 Enantioselective Synthesis of Fluoroalkyl-Substituted syn-Diamines by the
 Asymmetric gem-Difunctionalization of 2,2,2-Trifluorodiazoethane
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              4559
_journal_page_last               4565
_journal_paper_doi               10.1021/acscatal.0c00972
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H19 F5 N2'
_chemical_formula_sum            'C25 H19 F5 N2'
_chemical_formula_weight         442.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 108.3570(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.43000(10)
_cell_length_b                   11.61770(10)
_cell_length_c                   10.91800(10)
_cell_measurement_reflns_used    19825
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4930
_cell_measurement_theta_min      3.8050
_cell_volume                     1014.866(18)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.988
_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     26.00 120.00   0.50    0.05    --   46.62  70.00-139.00  188
  2  \w    -25.00  68.00   0.50    0.05    --   46.62 -70.00  89.00  186
  3  \w   -173.00 -79.00   0.50    0.05    -- -100.00 -70.00  89.00  188
  4  \w   -121.00 -27.00   0.50    0.05    -- -100.00  70.00-139.00  188
  5  \w     86.00 178.00   0.50    0.05    --  107.00  70.00-139.00  184
  6  \w     34.00 128.00   0.50    0.05    --  107.00 -70.00  89.00  188
  7  \w   -119.00 -71.00   0.50    0.05    --  -46.62-125.00 -60.00   96
  8  \w   -119.00 -71.00   0.50    0.05    --  -46.62-125.00-120.00   96
  9  \w    -67.00  26.00   0.50    0.05    --  -46.62  70.00-139.00  186
 10  \w    -62.00  29.00   0.50    0.05    --  -46.62  19.00-150.00  182
 11  \w   -119.00 -71.00   0.50    0.05    --  -46.62-125.00  60.00   96
 12  \w   -119.00 -71.00   0.50    0.05    --  -46.62-125.00 -90.00   96
 13  \w     32.00 120.00   0.50    0.05    --   46.62  38.00 -30.00  176
 14  \w   -173.00 -82.00   0.50    0.05    -- -100.00 -61.00 150.00  182
 15  \w   -117.00 -27.00   0.50    0.05    -- -100.00  61.00 -30.00  180
 16  \w   -172.00 -85.00   0.50    0.05    -- -100.00 -45.00 -30.00  174
 17  \w   -176.00 -82.00   0.50    0.05    -- -100.00 -15.00 -30.00  188
 18  \w   -172.00 -85.00   0.50    0.05    -- -100.00 -45.00 -60.00  174
 19  \w     34.00 117.00   0.50    0.05    --  107.00-125.00 120.00  166
 20  \w     93.00 178.00   0.50    0.05    --  107.00  45.00 -60.00  170
 21  \w     83.00 178.00   0.50    0.05    --  107.00  77.00 -30.00  190
 22  \w     90.00 178.00   0.50    0.05    --  107.00  61.00 -60.00  176
 23  \w     34.00 109.00   0.50    0.05    --  107.00 -94.00  60.00  150
 24  \w     34.00 109.00   0.50    0.05    --  107.00 -94.00 -60.00  150
 25  \w     34.00 125.00   0.50    0.05    --  107.00 -61.00-120.00  182
 26  \w     83.00 178.00   0.50    0.05    --  107.00  77.00-120.00  190
 27  \w     76.00 178.00   0.50    0.05    --  107.00 125.00 -30.00  204
 28  \w     34.00 109.00   0.50    0.05    --  107.00 -94.00-180.00  150
 29  \w     89.00 178.00   0.50    0.05    --  107.00  15.00-150.00  178
 30  \w     34.00 109.00   0.50    0.05    --  107.00 -94.00 -30.00  150
 31  \w     31.00 125.00   0.50    0.05    --  107.00 -15.00  90.00  188
 32  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00  60.00  192
 33  \w   -119.00 -23.00   0.50    0.05    --  -46.62 -77.00 120.00  192
 34  \w     32.00  94.00   0.50    0.05    --   46.62  38.00-180.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0399975000
_diffrn_orient_matrix_UB_12      0.0949110000
_diffrn_orient_matrix_UB_13      0.0842763000
_diffrn_orient_matrix_UB_21      0.1408638000
_diffrn_orient_matrix_UB_22      -0.0449357000
_diffrn_orient_matrix_UB_23      0.1177750000
_diffrn_orient_matrix_UB_31      0.1250497000
_diffrn_orient_matrix_UB_32      0.0809916000
_diffrn_orient_matrix_UB_33      -0.0335536000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0324
_diffrn_reflns_av_unetI/netI     0.0178
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            20728
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.735
_diffrn_reflns_theta_min         4.267
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.004
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61731
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.425
_refine_diff_density_rms         0.041
_refine_ls_abs_structure_details
;
 Flack x determined using 1904 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4176
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0317
_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^+0.3147P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0855
_refine_ls_wR_factor_ref         0.0857
_reflns_Friedel_coverage         0.873
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                4143
_reflns_number_total             4176
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs0c00972_si_002.cif
_cod_data_source_block           lijl_190314_2
_cod_depositor_comments          'Adding full bibliography for 4517527.cif.'
_cod_original_cell_volume        1014.865(18)
_cod_database_code               4517527
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.906
_shelx_estimated_absorpt_t_min   0.753
_reflns_odcompleteness_completeness 99.72
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
2.a Riding coordinates:
 N17(H17)
2.b Ternary CH refined with riding coordinates:
 C11(H11), C12(H12)
2.c Aromatic/amide H refined with riding coordinates:
 N18(H18), C20(H20), C23(H23), C2(H2), C28(H28), C27(H27), C4(H4), C9(H9),
 C24(H24), C8(H8), C6(H6), C31(H31), C7(H7), C21(H21), C3(H3), C30(H30)
;
_shelx_res_checksum              17793
_shelx_hkl_checksum              16926
_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 1.441
_oxdiff_exptl_absorpt_empirical_full_min 0.638