Palladium-catalyzed esterification reaction of arenes/heterocyclic carboxylic acids with difluoroallyl bromide for the efficient preparation of difluoroallyl esters.
Chen, Li; Li, Yang; Hu, Yun-Long; Chen, Xin; Chen, Mei-Ru; Zhang, Jin; Shi, Lan-Ting; Li, Hong; Organic & biomolecular chemistry 24 (2026) 1114–1119; doi:10.1039/d5ob01961c

data_7160955
_publ_section_title
;
 Palladium-catalyzed esterification reaction of arenes/heterocyclic
 carboxylic acids with difluoroallyl bromide for the efficient preparation
 of difluoroallyl esters.
;
_journal_issue                   5
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1114
_journal_page_last               1119
_journal_paper_doi               10.1039/d5ob01961c
_journal_volume                  24
_journal_year                    2026
_chemical_formula_moiety         'C13 H10 Cl F2 N O2'
_chemical_formula_sum            'C13 H10 Cl F2 N O2'
_chemical_formula_weight         285.67
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-12-24
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2025-06-15 deposited with the CCDC.	2026-01-14 downloaded from the CCDC.
;
_cell_angle_alpha                104.964(2)
_cell_angle_beta                 95.599(2)
_cell_angle_gamma                90.149(2)
_cell_formula_units_Z            4
_cell_length_a                   6.76030(10)
_cell_length_b                   13.7808(3)
_cell_length_c                   13.7988(4)
_cell_measurement_reflns_used    11687
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.0890
_cell_measurement_theta_min      4.0430
_cell_volume                     1235.49(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.121a 64-bit (release 24-04-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.121a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.932
_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     90.00 116.00   0.50    0.05    --   75.66  22.00  44.36   52
  2  \w     55.00  96.00   0.50    0.05    --   62.19  15.00 -30.00   82
  3  \w     63.00  88.00   0.50    0.05    --   62.19  15.00 -60.00   50
  4  \w     69.00 102.00   0.50    0.05    --   62.19  15.00-120.00   66
  5  \w     62.00  91.00   0.50    0.05    --   62.19  15.00-180.00   58
  6  \w     73.00 101.00   0.50    0.05    --   62.19  15.00-150.00   56
  7  \w     64.00 111.00   0.50    0.05    --   71.25  15.00-120.00   94
  8  \w     72.00 111.00   0.50    0.05    --   74.35  15.00 -90.00   78
  9  \w     80.00 107.00   0.50    0.05    --   71.25  15.00   0.00   54
 10  \w     59.00  86.00   0.50    0.05    --   62.19  15.00  30.00   54
 11  \w     72.00 103.00   0.50    0.05    --   62.19  15.00  90.00   62
 12  \w     72.00  99.00   0.50    0.05    --   74.35  15.00 150.00   54
 13  \w     76.00 107.00   0.50    0.05    --   71.25  15.00  90.00   62
 14  \w     82.00 112.00   0.50    0.05    --   74.35  15.00  30.00   60
 15  \w     77.00 112.00   0.50    0.05    --   74.35  15.00 -30.00   70
 16  \w     55.00  85.00   0.50    0.05    --   62.19  15.00 150.00   60
 17  \w     74.00 103.00   0.50    0.05    --   74.35  15.00 120.00   58
 18  \w     80.00 107.00   0.50    0.05    --   74.35  15.00 -60.00   54
 19  \w     78.00 107.00   0.50    0.05    --   74.35  15.00-150.00   58
 20  \w     71.00 109.00   0.50    0.05    --   74.35  15.00-180.00   76
 21  \w     43.00  83.00   0.50    0.05    --   74.35-125.00-150.00   80
 22  \w     27.00  75.00   0.50    0.05    --   62.19-125.00-180.00   96
 23  \w     44.00  76.00   0.50    0.05    --   62.19-125.00-120.00   64
 24  \w     26.00  78.00   0.50    0.05    --   62.19-125.00 -90.00  104
 25  \w     30.00  55.00   0.50    0.05    --   62.19-125.00 -30.00   50
 26  \w     28.00  54.00   0.50    0.05    --   62.19-125.00   0.00   52
 27  \w     29.00  77.00   0.50    0.05    --   62.19-125.00  30.00   96
 28  \w     34.00  76.00   0.50    0.05    --   62.19-125.00  60.00   84
 29  \w     28.00  70.00   0.50    0.05    --   62.19-125.00 120.00   84
 30  \w     44.00  70.00   0.50    0.05    --   62.19-125.00 150.00   52
 31  \w     51.00  87.00   0.50    0.05    --   71.25-125.00 120.00   72
 32  \w     57.00  90.00   0.50    0.05    --   74.35-125.00  60.00   66
 33  \w     59.00  86.00   0.50    0.05    --   71.25-125.00  30.00   54
 34  \w     44.00  89.00   0.50    0.05    --   74.35-125.00   0.00   90
 35  \w     48.00  83.00   0.50    0.05    --   71.25-125.00 -60.00   70
 36  \w     59.00  85.00   0.50    0.05    --   71.25-125.00-120.00   52
 37  \w     43.00  90.00   0.50    0.05    --   74.35-125.00-180.00   94
 38  \w     54.00  88.00   0.50    0.05    --   74.35-125.00-120.00   68
 39  \w     65.00  90.00   0.50    0.05    --   74.35-125.00 -60.00   50
 40  \w     51.00  90.00   0.50    0.05    --   74.35-125.00 -30.00   78
 41  \w     38.00  63.00   0.50    0.05    --   74.35-125.00  30.00   50
 42  \w     42.00  89.00   0.50    0.05    --   74.35-125.00  90.00   94
 43  \w     45.00  88.00   0.50    0.05    --   74.35-125.00 150.00   86
 44  \w     65.00  90.00   0.50    0.05    --   74.35-125.00 120.00   50
 45  \w     39.00  89.00   0.50    0.05    --   74.35-125.00 -90.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0228472000
_diffrn_orient_matrix_UB_12      0.0475488000
_diffrn_orient_matrix_UB_13      -0.0898564000
_diffrn_orient_matrix_UB_21      0.1053269000
_diffrn_orient_matrix_UB_22      -0.0895680000
_diffrn_orient_matrix_UB_23      -0.0639176000
_diffrn_orient_matrix_UB_31      -0.2021336000
_diffrn_orient_matrix_UB_32      -0.0558373000
_diffrn_orient_matrix_UB_33      -0.0365346000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.932
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15477
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.932
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.224
_diffrn_reflns_theta_min         4.049
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.976
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77131
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.121a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.536
_exptl_crystal_description       block
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.772
_refine_diff_density_min         -0.527
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     353
_refine_ls_number_reflns         4607
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0765P)^2^+2.6052P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1503
_refine_ls_wR_factor_ref         0.1514
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4327
_reflns_number_total             4607
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01961c2.cif
_cod_data_source_block           ly257
_cod_database_code               7160955
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S F'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C12-H12A
 0.985 with sigma of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C6(H6), C7(H7), C11(H11), C14(H14), C16(H16), C19(H19),
 C20(H20), C24(H24)
3.b X=CH2 refined with riding coordinates:
 C25(H25A,H25B)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C38(H38A,H38B,H38C)
;
_shelx_res_checksum              58095
_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 1.385
_oxdiff_exptl_absorpt_empirical_full_min 0.532