Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles.
Wu, Jia-Qiang; Zhang, Shang-Shi; Gao, Hui; Qi, Zisong; Zhou, Chu-Jun; Ji, Wei-Wei; Liu, Yao; Chen, Yunyun; Li, Qingjiang; Li, Xingwei; Wang, Honggen; Journal of the American Chemical Society  (2017) –; doi:10.1021/jacs.7b00118

data_4125487
_publ_section_title
;
 Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of
 Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of
 Fluorinated Heterocycles.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.7b00118
_journal_year                    2017
_chemical_formula_moiety         'C10 H9 F2 N O2'
_chemical_formula_sum            'C10 H9 F2 N O2'
_chemical_formula_weight         213.18
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-05-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 95.3562(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   11.53896(15)
_cell_length_b                   7.57923(11)
_cell_length_c                   20.9318(3)
_cell_measurement_reflns_used    6567
_cell_measurement_temperature    103(2)
_cell_measurement_theta_max      72.5740
_cell_measurement_theta_min      2.1070
_cell_volume                     1822.63(4)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      103(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2417
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.959
_diffrn_measured_fraction_theta_max 0.959
_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    -58.00  21.00   1.00    1.50    --  -44.02  38.00  90.00   79
  2  \w    -98.00 -72.00   1.00    3.00    --  -90.00 -39.00-161.00   26
  3  \w   -129.00-103.00   1.00    3.00    --  -90.00 -39.00-161.00   26
  4  \w   -125.00 -80.00   1.00    1.50    --  -44.02 -99.00 -30.00   45
  5  \w   -123.00 -79.00   1.00    1.50    --  -44.02 -99.00  60.00   44
  6  \w     85.00 111.00   1.00    1.50    --   44.02 125.00-180.00   26
  7  \w     77.00 171.00   1.00    3.00    --  100.00  45.00 -60.00   94
  8  \w    146.00 171.00   1.00    3.00    --  100.00  45.00 120.00   25
  9  \w     78.00 120.00   1.00    3.00    --  100.00  45.00 120.00   42
 10  \w     78.00 164.00   1.00    3.00    --  100.00  30.00  60.00   86
 11  \w     77.00 123.00   1.00    3.00    --  100.00 -61.00  30.00   46
 12  \w     30.00 122.00   1.00    3.00    --  100.00 -61.00 -30.00   92
 13  \w   -136.00-111.00   1.00    3.00    --  -90.00-125.00   0.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1276225000
_diffrn_orient_matrix_UB_12      0.0552797000
_diffrn_orient_matrix_UB_13      -0.0038641000
_diffrn_orient_matrix_UB_21      -0.0222843000
_diffrn_orient_matrix_UB_22      0.1720235000
_diffrn_orient_matrix_UB_23      0.0360454000
_diffrn_orient_matrix_UB_31      0.0343852000
_diffrn_orient_matrix_UB_32      -0.0932786000
_diffrn_orient_matrix_UB_33      0.0644181000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0173
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            7908
_diffrn_reflns_theta_full        72.25
_diffrn_reflns_theta_max         72.25
_diffrn_reflns_theta_min         4.24
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Nova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.177
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56316
_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            colorless
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             880
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.512
_refine_diff_density_min         -0.430
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     273
_refine_ls_number_reflns         3450
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0408
_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^)+(0.0614P)^2^+1.0299P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1062
_refine_ls_wR_factor_ref         0.1074
_reflns_number_gt                3299
_reflns_number_total             3450
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja7b00118_si_002.cif
_cod_data_source_block           zss_160510_2
_cod_database_code               4125487
_reflns_odcompleteness_completeness 99.01
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C25(H25), C28(H28)
2.b Aromatic/amide H refined with riding coordinates:
 N9(H9), N10(H10), C11(H11), C12(H12), C14(H14), C17(H17), C19(H19), C26(H26),
 C27(H27), C29(H29)
2.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C23(H23A,H23B,H23C)
;
_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 1.668
_oxdiff_exptl_absorpt_empirical_full_min 0.618