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_7134747
_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 S
_chemical_formula_moiety         'C11 H9 Br F3 N O'
_chemical_formula_sum            'C11 H9 Br F3 N O'
_chemical_formula_weight         308.10
_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             2024-04-24
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-09-16 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                   7.084(3)
_cell_length_b                   10.507(5)
_cell_length_c                   16.180(8)
_cell_measurement_reflns_used    7980
_cell_measurement_temperature    295.00
_cell_measurement_theta_max      26.452
_cell_measurement_theta_min      2.311
_cell_volume                     1204.3(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      295.00
_diffrn_measured_fraction_theta_full 0.973
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0476
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            17814
_diffrn_reflns_point_group_measured_fraction_full 0.976
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.452
_diffrn_reflns_theta_min         2.311
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.434
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.4603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1279 before and 0.0765 after correction.
The Ratio of minimum to maximum transmission is 0.6175.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.102
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Flack x determined using 745 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.048(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     156
_refine_ls_number_reflns         2419
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0265
_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^)+(0.0319P)^2^+0.0498P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0589
_refine_ls_wR_factor_ref         0.0630
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                1994
_reflns_number_total             2419
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc01559f2.cif
_cod_data_source_block           nsbromo_0m_a
_cod_depositor_comments
'Adding full bibliography for 7134747--7134749.cif.'
_cod_database_code               7134747
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.721
_shelx_estimated_absorpt_t_min   0.519
_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.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C4(H4), C6(H6)
2.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C9(H9A,H9B,H9C)
;
_shelx_res_checksum              51877
_shelx_hkl_checksum              25480
_olex2_submission_special_instructions 'No special instructions were received'