Electrochemically Cooperative Halogen Cation Delivery Enables Modular Electrophilic Haloesterification of Both Activated and Unactivated Alkenes
Xu, Hehuan; Qian, Duo-Duo; Fan, Yi; Zhang, Jia-Jia; Guo, Chang-Le; Xu, Hai-Chao; Chemical Science  (2026) –; doi:10.1039/D6SC00279J

data_1576902
_publ_section_title
;
 Electrochemically cooperative halogen-cation delivery enables modular
 electrophilic haloesterification of both activated and unactivated
 alkenes.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              9684
_journal_page_last               9694
_journal_paper_doi               10.1039/d6sc00279j
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C28 H29 Br O5'
_chemical_formula_sum            'C28 H29 Br O5'
_chemical_formula_weight         525.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-06
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-08-21 deposited with the CCDC.	2026-03-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.499(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.7657(4)
_cell_length_b                   10.2109(4)
_cell_length_c                   12.7242(7)
_cell_measurement_reflns_used    3350
_cell_measurement_temperature    170.00(10)
_cell_measurement_theta_max      70.9970
_cell_measurement_theta_min      4.3350
_cell_volume                     1238.74(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      170.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -93.00 -20.00   1.00    1.89    --  -35.37 -57.00 120.00   73
  2  \w    -99.00 -55.00   1.00    1.89    --  -35.37 -57.00  30.00   44
  3  \w     31.00  72.00   1.00    1.89    --   35.37 -99.00 120.00   41
  4  \w      6.00 103.00   1.00    1.89    --   35.37  19.00 -90.00   97
  5  \w     14.00  71.00   1.00    1.89    --   35.37 -99.00   0.00   57
  6  \w    -32.00  52.00   1.00    1.89    --   35.37 -38.00 -90.00   84
  7  \w     28.00  94.00   1.00    1.89    --   35.37  57.00  90.00   66
  8  \w     23.00  73.00   1.00    1.89    --   35.37 -99.00-120.00   50
  9  \w     52.00 108.00   1.00    7.56    --  106.81-111.00 -90.00   56
 10  \w     81.00 108.00   1.00    7.56    --  106.81-111.00 -30.00   27
 11  \w     40.00 125.00   1.00    7.56    --  106.81 -61.00-180.00   85
 12  \w     69.00 160.00   1.00    7.56    --  106.81  15.00 -60.00   91
 13  \w    126.00 173.00   1.00    7.56    --  106.81  61.00 -30.00   47
 14  \w     46.00 119.00   1.00    7.56    --  106.81 -61.00 -90.00   73
 15  \w     90.00 122.00   1.00    7.56    --  106.81  61.00 -30.00   32
 16  \w    103.00 175.00   1.00    7.56    --  106.81  45.00   0.00   72
 17  \w     41.00  91.00   1.00    7.56    --  106.81-111.00-150.00   50
 18  \w     37.00 111.00   1.00    7.56    --  106.81 -30.00 -30.00   74
 19  \w     54.00 126.00   1.00    7.56    --  106.81 -30.00  30.00   72
 20  \w     40.00 105.00   1.00    7.56    --  106.81 -61.00  60.00   65
 21  \w     64.00  96.00   1.00    7.56    --  106.81 178.00  60.00   32
 22  \w     67.00 107.00   1.00    7.56    --  106.81-111.00  90.00   40
 23  \w     90.00 128.00   1.00    7.56    --  106.81 -77.00 -60.00   38
 24  \w     81.00 109.00   1.00    7.56    --  106.81-112.00 168.61   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0091574000
_diffrn_orient_matrix_UB_12      -0.0882014000
_diffrn_orient_matrix_UB_13      0.0964913000
_diffrn_orient_matrix_UB_21      0.0319630000
_diffrn_orient_matrix_UB_22      0.1188153000
_diffrn_orient_matrix_UB_23      0.0758529000
_diffrn_orient_matrix_UB_31      -0.1581922000
_diffrn_orient_matrix_UB_32      0.0291953000
_diffrn_orient_matrix_UB_33      -0.0176966000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0523
_diffrn_reflns_av_unetI/netI     0.0597
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6243
_diffrn_reflns_point_group_measured_fraction_full 0.816
_diffrn_reflns_point_group_measured_fraction_max 0.816
_diffrn_reflns_theta_full        59.995
_diffrn_reflns_theta_max         59.995
_diffrn_reflns_theta_min         3.558
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.560
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.409
_exptl_crystal_description       needle
_exptl_crystal_F_000             544
_refine_diff_density_max         1.639
_refine_diff_density_min         -0.563
_refine_diff_density_rms         0.182
_refine_ls_abs_structure_details
;
 Flack x determined using 613 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.18(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.662
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         2992
_refine_ls_number_restraints     319
_refine_ls_restrained_S_all      1.648
_refine_ls_R_factor_all          0.1558
_refine_ls_R_factor_gt           0.1362
_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          0.3908
_refine_ls_wR_factor_ref         0.4017
_reflns_Friedel_coverage         0.538
_reflns_Friedel_fraction_full    0.610
_reflns_Friedel_fraction_max     0.610
_reflns_number_gt                2404
_reflns_number_total             2992
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6sc00279j3.cif
_cod_data_source_block           gcl-20250730_auto
_cod_depositor_comments          'Adding full bibliography for 1576902.cif.'
_cod_database_code               1576902
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C1 H1 O1 N1'
_diffrn_oxdiff_digest_frames
;
01f4cff74926875d59958121b32265d7b600029db1e
;
_diffrn_oxdiff_digest_hkl
;
019127f5dc9f2a70dcb4ecdba651269f8062e5
;
_reflns_odcompleteness_completeness 99.87
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C22-O5
 1.2 with sigma of 0.02
 O4-C22
 1.2 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01
5.a Ternary CH refined with riding coordinates:
 C6(H6), C11(H11), C5(H5), C21(H21), C20(H20)
5.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C7(H7A,H7B), C1(H1A,H1B), C2(H2A,H2B), C8(H8A,H8B), C13(H13A,
 H13B)
5.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C18(H18), C24(H24), C15(H15), C28(H28), C25(H25), C17(H17),
 C27(H27), C22(H22)
5.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C)
;
_shelx_res_checksum              20503
_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 2.382
_oxdiff_exptl_absorpt_empirical_full_min 0.661