Pd-catalyzed enantioselective reductive Heck reaction of mono-fluoro, <i>gem</i>-difluoro, and trifluoromethyl tethered-alkenes.
Sihag, Naveen; Bhartiya, Hemaang; Jain, Swati; Singh, Jitendra; Reddy, S. Rajagopala; Yadav, M. Ramu; Chemical communications (Cambridge, England) 61 (2025) 11413–11416; doi:10.1039/d5cc01559f

data_7134748
_publ_section_title
;
 Pd-catalyzed enantioselective reductive Heck reaction of mono-fluoro,
 <i>gem</i>-difluoro, and trifluoromethyl tethered-alkenes.
;
_journal_issue                   61
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              11413
_journal_page_last               11416
_journal_paper_doi               10.1039/d5cc01559f
_journal_volume                  61
_journal_year                    2025
_chemical_absolute_configuration R
_chemical_formula_moiety         'C11 H10 Br F2 N O'
_chemical_formula_sum            'C11 H10 Br F2 N O'
_chemical_formula_weight         290.11
_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   geom
_audit_creation_date             2024-12-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-03 deposited with the CCDC.	2025-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.2114(5)
_cell_length_b                   8.6463(5)
_cell_length_c                   17.6697(11)
_cell_measurement_reflns_used    2105
_cell_measurement_temperature    100
_cell_measurement_theta_max      81.420
_cell_measurement_theta_min      5.006
_cell_volume                     1101.74(12)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.961
_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     67.00  92.00   0.50    1.15    --  115.25 -77.00 150.00   50
  2  \w     77.00 102.00   0.50    1.15    --  115.25 -77.00 -30.00   50
  3  \w     50.00  84.00   0.50    1.15    --  115.25 -77.00 -60.00   68
  4  \w     54.00  94.00   0.50    1.15    --  115.25 -77.00-180.00   80
  5  \w     48.00  80.00   0.50    0.50    --   47.17 -99.00 -60.00   64
  6  \w     59.00 109.00   0.50    1.15    --  115.25-125.00  30.00  100
  7  \w     46.00  97.00   0.50    1.15    --  115.25 -99.00 -60.00  102
  8  \w    111.00 171.00   0.50    1.15    --  115.25  44.00 -53.00  120
  9  \w    107.00 170.00   0.50    1.15    --  115.25  87.00 150.00  126
 10  \w     -4.00  23.00   0.50    0.50    --   47.17 -19.00 -90.00   54
 11  \w    -24.00  21.00   0.50    0.50    --   47.17 -19.00  30.00   90
 12  \w    -24.00   1.00   0.50    0.50    --   47.17 -44.00 155.00   50
 13  \w      5.00  47.00   0.50    0.50    --   47.17 -44.00 155.00   84
 14  \w    -68.00 -37.00   0.50    1.15    --  -97.00  61.00  90.00   62
 15  \w    -53.00 -27.00   0.50    1.15    --  -97.00  45.00 150.00   52
 16  \w    -54.00 -29.00   0.50    1.15    --  -97.00  45.00 -30.00   50
 17  \w    -53.00 -28.00   0.50    1.15    --  -97.00  44.00 -53.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  CrysAlisPro
_diffrn_measurement_method       '\f and \w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2011061000
_diffrn_orient_matrix_UB_12      -0.0600037000
_diffrn_orient_matrix_UB_13      -0.0037192000
_diffrn_orient_matrix_UB_21      -0.0240608000
_diffrn_orient_matrix_UB_22      -0.0763866000
_diffrn_orient_matrix_UB_23      0.0781098000
_diffrn_orient_matrix_UB_31      -0.0686152000
_diffrn_orient_matrix_UB_32      -0.1492409000
_diffrn_orient_matrix_UB_33      -0.0384854000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0800
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       4
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            4283
_diffrn_reflns_point_group_measured_fraction_full 0.933
_diffrn_reflns_point_group_measured_fraction_max 0.864
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         81.420
_diffrn_reflns_theta_min         5.006
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.180
_exptl_absorpt_correction_T_max  0.642
_exptl_absorpt_correction_T_min  0.436
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            colourless
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.749
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.134
_exptl_crystal_size_min          0.094
_refine_diff_density_max         1.366
_refine_diff_density_min         -1.443
_refine_diff_density_rms         0.184
_refine_ls_abs_structure_details
;
 Flack x determined using 627 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.171
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     129
_refine_ls_number_reflns         2105
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.171
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0649
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1286P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1857
_refine_ls_wR_factor_ref         0.1874
_reflns_Friedel_coverage         0.532
_reflns_Friedel_fraction_full    0.843
_reflns_Friedel_fraction_max     0.726
_reflns_number_gt                1961
_reflns_number_total             2105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01559f2.cif
_cod_data_source_block           ns-4-br_auto
_cod_depositor_comments
'Adding full bibliography for 7134747--7134749.cif.'
_cod_database_code               7134748
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         CHFBrON
_shelx_estimated_absorpt_t_max   0.642
_shelx_estimated_absorpt_t_min   0.436
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C11) = Uanis(C9)
Uanis(C2) = Uanis(C7)
Uanis(N1) = Uanis(C5)
3.a Ternary CH refined with riding coordinates:
 C10(H10)
3.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C6(H6), C5(H5)
3.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C11(H11A,H11B,H11C)
;
_shelx_res_checksum              52625
_shelx_hkl_checksum              76816
_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 2.832
_oxdiff_exptl_absorpt_empirical_full_min 0.268