Ruthenium(ii)-catalyzed selective C-H difluoroalkylation of aniline derivatives with pyrimidyl auxiliaries.
Wang, Xin-Gang; Li, Yuke; Zhang, Lu-Lu; Zhang, Bo-Sheng; Wang, Qiang; Ma, Jun-Wei; Liang, Yong-Min; Chemical communications (Cambridge, England) 54 (2018) 9541–9544; doi:10.1039/c8cc05067h

data_7122077
_publ_section_title
;
 Ruthenium(ii)-catalyzed selective C-H difluoroalkylation of aniline
 derivatives with pyrimidyl auxiliaries.
;
_journal_issue                   68
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              9541
_journal_page_last               9544
_journal_paper_doi               10.1039/c8cc05067h
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C15 H15 F2 N3 O3'
_chemical_formula_sum            'C15 H15 F2 N3 O3'
_chemical_formula_weight         323.30
_chemical_name_systematic
'ethyl 2,2-difluoro-2-(2-methoxy-4-(pyrimidin-2-ylamino)phenyl)acetate'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2018-03-06
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2018-03-06 deposited with the CCDC.
2018-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                63.165(6)
_cell_angle_beta                 62.666(7)
_cell_angle_gamma                64.519(6)
_cell_formula_units_Z            4
_cell_length_a                   12.5999(8)
_cell_length_b                   12.8512(7)
_cell_length_c                   13.5479(9)
_cell_measurement_reflns_used    4498
_cell_measurement_temperature    289.7(5)
_cell_measurement_theta_max      69.7510
_cell_measurement_theta_min      3.9940
_cell_volume                     1668.7(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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      289.7(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0733
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.958
_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    -25.00  18.00   1.00    1.00    --    0.00 -57.00  90.00   43
  2  \w      1.00  27.00   1.00    1.00    --   54.00 -57.00 120.00   26
  3  \w     65.00 114.00   1.00    1.00    --  108.00-111.00  90.00   49
  4  \w     62.00  93.00   1.00    1.00    --  108.00 -91.00 150.00   31
  5  \w     41.00 130.00   1.00    1.00    --  108.00 -50.00  90.00   89
  6  \w     82.00 125.00   1.00    1.00    --  108.00  38.00 -30.00   43
  7  \w     74.00 159.00   1.00    1.00    --  108.00  25.00 -90.00   85
  8  \w    115.00 141.00   1.00    1.00    --  108.00 111.00-150.00   26
  9  \w     58.00 129.00   1.00    1.00    --  108.00 178.00-150.00   71
 10  \w     28.00  62.00   1.00    1.00    --    0.00  57.00-120.00   34
 11  \w     11.00 127.00   1.00    1.00    --   54.00  19.00-120.00  116
 12  \w    110.00 136.00   1.00    1.00    --  108.00 -91.00 -90.00   26
 13  \w     63.00 112.00   1.00    1.00    --  108.00-111.00-120.00   49
 14  \w     63.00  89.00   1.00    1.00    --  108.00 -91.00 -90.00   26
 15  \w     43.00 130.00   1.00    1.00    --  108.00 -50.00 -30.00   87
 16  \w     44.00 125.00   1.00    1.00    --  108.00 -50.00-180.00   81
 17  \w     40.00 110.00   1.00    1.00    --  108.00  12.00-120.00   70
 18  \w     43.00 139.00   1.00    1.00    --  108.00 -25.00 -90.00   96
 19  \w     37.00 104.00   1.00    1.00    --   54.00-125.00-120.00   67
 20  \w     37.00 103.00   1.00    1.00    --  108.00-111.00   0.00   66
 21  \w     -1.00  68.00   1.00    1.00    --   54.00 -57.00-120.00   69
 22  \w    -10.00  20.00   1.00    1.00    --    0.00  57.00-120.00   30
 23  \w    -64.00 -39.00   1.00    1.00    --    0.00 144.00-136.00   25
 24  \w     29.00 118.00   1.00    1.00    --   54.00  77.00  90.00   89
 25  \w    -14.00  71.00   1.00    1.00    --   54.00 -57.00 -30.00   85
 26  \w    -68.00 -35.00   1.00    1.00    --    0.00 -57.00  90.00   33
;
_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      0.0079519000
_diffrn_orient_matrix_UB_12      0.0694884000
_diffrn_orient_matrix_UB_13      -0.1291281000
_diffrn_orient_matrix_UB_21      0.1267288000
_diffrn_orient_matrix_UB_22      -0.0911931000
_diffrn_orient_matrix_UB_23      -0.0386542000
_diffrn_orient_matrix_UB_31      -0.0666899000
_diffrn_orient_matrix_UB_32      -0.0803325000
_diffrn_orient_matrix_UB_33      0.0066299000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0583
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10134
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         69.983
_diffrn_reflns_theta_min         3.872
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.907
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53394
_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 dark yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM/PE'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.404
_refine_diff_density_min         -0.440
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.169
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     419
_refine_ls_number_reflns         6075
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.193
_refine_ls_R_factor_all          0.0990
_refine_ls_R_factor_gt           0.0789
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2500
_refine_ls_wR_factor_ref         0.3102
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4455
_reflns_number_total             6075
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05067h2.cif
_cod_data_source_block           wangxg_0306
_cod_depositor_comments          'Adding full bibliography for 7122077.cif.'
_cod_database_code               7122077
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 97.97
_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, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(O6) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C29(H29A,H29B)
3.b Aromatic/amide H refined with riding coordinates:
 N3(H3), C1(H1), C2(H2), C3(H3A), C6(H6), C9(H9), C10(H10), N6(H6A), C16(H16),
 C17(H17), C18(H18), C21(H21), C24(H24), C25(H25)
3.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C26(H26A,H26B,H26C), C30(H30A,H30B,
 H30C)
;
_olex2_date_sample_data_collection 2018-03-06
_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 2.196
_oxdiff_exptl_absorpt_empirical_full_min 0.583