Amides as modifiable directing groups in electrophilic borylation.
Iqbal, Saqib A.; Uzelac, Marina; Nawaz, Ismat; Wang, Zhongxing; Jones, T. Harri; Yuan, Kang; Millet, Clement R. P.; Nichol, Gary S.; Chotana, Ghayoor Abbas; Ingleson, Michael J.; Chemical science 14 (2023) 3865–3872; doi:10.1039/d2sc06483a

data_1568668
_publ_section_title
;
 Amides as modifiable directing groups in electrophilic borylation.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              3865
_journal_page_last               3872
_journal_paper_doi               10.1039/d2sc06483a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'B Br4, C H2 Cl2, C22 H21 B N O'
_chemical_formula_sum            'C23 H23 B2 Br4 Cl2 N O'
_chemical_formula_weight         741.58
_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
_audit_creation_date             2022-11-22
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-22 deposited with the CCDC.	2023-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                107.814(3)
_cell_angle_beta                 93.035(2)
_cell_angle_gamma                97.768(2)
_cell_formula_units_Z            2
_cell_length_a                   7.3365(2)
_cell_length_b                   12.5616(4)
_cell_length_c                   15.3464(4)
_cell_measurement_reflns_used    10163
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      28.8650
_cell_measurement_theta_min      3.6940
_cell_volume                     1327.45(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      120.00
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.895
_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    -33.00  53.00   1.00   30.00    --  -15.66  46.00-138.00   86
  2  \w    -51.00  35.00   1.00   30.00    --   17.38 -46.00  72.00   86
  3  \w      0.00  86.00   1.00   30.00    --   17.38  46.00-138.00   86
  4  \w    -42.00  39.00   1.00   30.00    --  -15.66  77.00 -30.00   81
  5  \w     39.00  90.00   1.00   30.00    --   17.38 178.00  60.00   51
  6  \w      1.00  85.00   1.00   30.00    --   17.38  57.00-120.00   84
  7  \w     -9.00  39.00   1.00   30.00    --   17.38  77.00  90.00   48
  8  \w     -9.00  39.00   1.00   30.00    --   17.38  77.00 -60.00   48
  9  \w      1.00  85.00   1.00   30.00    --   17.38  57.00 120.00   84
 10  \w    -20.00  56.00   1.00   30.00    --   17.38 -99.00 150.00   76
 11  \w    -20.00  56.00   1.00   30.00    --   17.38 -99.00 -90.00   76
 12  \w     -9.00  39.00   1.00   30.00    --   17.38  77.00  30.00   48
 13  \w    -20.00  52.00   1.00   30.00    --   17.38 -99.00  30.00   72
 14  \w     -9.00  39.00   1.00   30.00    --   17.38  77.00   0.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0351
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.895
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            29275
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.895
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.326
_diffrn_reflns_theta_min         3.451
_exptl_absorpt_coefficient_mu    6.283
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78770
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.855
_exptl_crystal_description       plate
_exptl_crystal_F_000             720
_exptl_crystal_recrystallization_method
'Crystallised at room temperature from DCM solution.'
_exptl_crystal_size_max          0.253
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.124
_refine_diff_density_max         0.516
_refine_diff_density_min         -0.483
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     316
_refine_ls_number_reflns         6510
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0444
_refine_ls_R_factor_gt           0.0286
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0204P)^2^+1.0297P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0551
_refine_ls_wR_factor_ref         0.0593
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5260
_reflns_number_total             6510
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06483a2.cif
_cod_data_source_block           mu734_reprocess
_cod_depositor_comments
'Adding full bibliography for 1568667--1568672.cif.'
_cod_database_code               1568668
_shelx_shelxl_version_number     2018/3
_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
 Br4-B2 \\sim Br4A-B2
 with sigma of 0.02
3. Others
 Sof(Br4A)=1-FVAR(1)
 Sof(Br4)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B)
4.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C5(H5), C10(H10), C4(H4), C11(H11), C17(H17), C15(H15), C16(H16)
4.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              6298
_shelx_hkl_checksum              93247
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_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
;