Regioselective <i>ortho</i> halogenation of <i>N</i>-aryl amides and ureas <i>via</i> oxidative halodeboronation: harnessing boron reactivity for efficient C-halogen bond installation.
Shinde, Ganesh H.; Ghotekar, Ganesh S.; Amombo Noa, Francoise M.; Öhrström, Lars; Norrby, Per-Ola; Sundén, Henrik; Chemical science 14 (2023) 13429–13436; doi:10.1039/d3sc04628a

data_1570170
_publ_section_title
;
 Regioselective <i>ortho</i> halogenation of <i>N</i>-aryl amides and
 ureas <i>via</i> oxidative halodeboronation: harnessing boron reactivity
 for efficient C-halogen bond installation.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              13429
_journal_page_last               13436
_journal_paper_doi               10.1039/d3sc04628a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C11 H14 B F2 N O'
_chemical_formula_sum            'C11 H14 B F2 N O'
_chemical_formula_weight         225.04
_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             2023-07-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-07-12 deposited with the CCDC.	2023-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.4333(2)
_cell_length_b                   11.2099(3)
_cell_length_c                   15.6487(5)
_cell_measurement_reflns_used    4281
_cell_measurement_temperature    101(3)
_cell_measurement_theta_max      75.2860
_cell_measurement_theta_min      4.8470
_cell_volume                     1128.53(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_diffrn_ambient_temperature      101(3)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.978
_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   -123.00 -29.00   0.50    2.21    --  -43.19 -16.00 -23.00  188
  2  \w     15.00  88.00   0.50    2.21    --   43.19-118.00-110.00  146
  3  \w     33.00 123.00   0.50    2.21    --   43.19  16.00 146.00  180
  4  \w   -136.00 -90.00   0.50    8.82    -- -104.50 -16.00 -23.00   92
  5  \w     33.00  97.00   0.50    8.82    --  108.62-115.00 156.00  128
  6  \w     94.00 143.00   0.50    8.82    --  108.62  16.00 146.00   98
  7  \w     33.00  97.00   0.50    8.82    --  108.62-118.00-110.00  128
  8  \w    -15.00  34.00   0.50    2.21    --  -43.19  38.00-180.00   98
  9  \w    -72.00 -30.00   0.50    8.82    -- -104.50  77.00   0.00   84
 10  \w   -132.00 -89.00   0.50    8.82    -- -104.50 -15.00-180.00   86
 11  \w   -174.00 -91.00   0.50    8.82    -- -104.50 -52.00   4.66  166
 12  \w    -72.00 -30.00   0.50    8.82    -- -104.50  77.00-120.00   84
 13  \w   -132.00 -89.00   0.50    8.82    -- -104.50 -15.00-150.00   86
 14  \w    -72.00 -30.00   0.50    8.82    -- -104.50  77.00  60.00   84
 15  \w   -101.00 -31.00   0.50    8.82    -- -104.50 125.00-180.00  140
 16  \w   -132.00 -89.00   0.50    8.82    -- -104.50 -15.00 -90.00   86
 17  \w    -72.00 -30.00   0.50    8.82    -- -104.50  77.00  90.00   84
 18  \w    -92.00 -31.00   0.50    8.82    -- -104.50  92.00-107.02  122
 19  \w     34.00  92.00   0.50    8.82    --  108.62 -95.00 -60.00  116
 20  \w     35.00  79.00   0.50    8.82    --  108.62 -77.00 -60.00   88
 21  \w    -54.00 -28.00   0.50    2.21    --  -43.19 -59.00  24.01   52
 22  \w    -54.00 -28.00   0.50    2.21    --  -43.19 -57.00 144.93   52
 23  \w    -54.00 -28.00   0.50    2.21    --  -43.19 -58.00 -59.78   52
 24  \w    -54.00 -28.00   0.50    2.21    --  -43.19 -56.00-142.05   52
 25  \w    -54.00 -28.00   0.50    2.21    --  -43.19 -59.00 -99.43   52
 26  \w    -15.00  34.00   0.50    2.21    --  -43.19  38.00  90.00   98
 27  \w   -132.00 -91.00   0.50    8.82    -- -104.50 -15.00 -60.00   82
 28  \w   -132.00 -89.00   0.50    8.82    -- -104.50 -15.00-120.00   86
 29  \w   -132.00 -89.00   0.50    8.82    -- -104.50 -15.00 150.00   86
 30  \w     94.00 139.00   0.50    8.82    --  108.62  15.00  90.00   90
 31  \w     94.00 139.00   0.50    8.82    --  108.62  15.00 120.00   90
 32  \w     94.00 139.00   0.50    8.82    --  108.62  15.00  60.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0851
_diffrn_reflns_av_unetI/netI     0.0465
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10669
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.623
_diffrn_reflns_theta_min         4.853
_exptl_absorpt_coefficient_mu    0.891
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62173
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_description       needle
_exptl_crystal_F_000             472
_exptl_crystal_size_max          0.26
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.290
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 601 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     179
_refine_ls_number_reflns         2261
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1000
_refine_ls_R_factor_gt           0.0921
_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^)+(0.0681P)^2^+2.5060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2193
_refine_ls_wR_factor_ref         0.2244
_reflns_Friedel_coverage         0.679
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                1972
_reflns_number_total             2261
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04628a2.cif
_cod_data_source_block           ggothersolvent_auto
_cod_depositor_comments          'Adding full bibliography for 1570170.cif.'
_cod_database_code               1570170
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.801
_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. Restrained distances
 C7-C1A \\sim C7-C1B
 with sigma of 0.02
 C7-C2A \\sim C7-C2B
 with sigma of 0.02
 C7-C3A \\sim C7-C3B
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C1B, C2B, C3B, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C3A, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=1-FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C11(H11), C12(H12), C13(H13), C14(H14)
5.b Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,
 H2BC), C3A(H3AA,H3AB,H3AC), C3B(H3BA,H3BB,H3BC)
;
_shelx_res_checksum              92781
_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
;