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_1568670
_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, C24 H23 B N O, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C24.5 H24 B2 Br4 Cl N O'
_chemical_formula_weight         725.16
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 117.156(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.5337(11)
_cell_length_b                   9.0190(3)
_cell_length_c                   18.6811(8)
_cell_measurement_reflns_used    6892
_cell_measurement_temperature    120.01(13)
_cell_measurement_theta_max      25.7550
_cell_measurement_theta_min      3.9100
_cell_volume                     2628.5(3)
_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 0.998
_diffrn_measured_fraction_theta_max 0.883
_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    -41.00  52.00   1.00   20.00    --  -15.66  75.00  81.00   93
  2  \w    -83.00  10.00   1.00   20.00    --  -15.66 -75.00 -46.00   93
  3  \w    -42.00  39.00   1.00   20.00    --  -15.66  77.00 -30.00   81
  4  \w    -88.00 -39.00   1.00   20.00    --  -15.66-178.00 120.00   49
  5  \w     -9.00  39.00   1.00   20.00    --   17.38  77.00 120.00   48
  6  \w     -9.00  39.00   1.00   20.00    --   17.38  77.00 -90.00   48
  7  \w     -9.00  39.00   1.00   20.00    --   17.38  77.00-150.00   48
  8  \w    -32.00  42.00   1.00   20.00    --  -15.66  57.00-120.00   74
;
_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  0.0517
_diffrn_reflns_av_unetI/netI     0.0591
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            29847
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.341
_diffrn_reflns_theta_min         3.261
_exptl_absorpt_coefficient_mu    6.245
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49581
_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 light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.832
_exptl_crystal_description       plate
_exptl_crystal_F_000             1412
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.222
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.957
_refine_diff_density_min         -1.261
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     319
_refine_ls_number_reflns         6372
_refine_ls_number_restraints     56
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0913
_refine_ls_R_factor_gt           0.0497
_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^)+(0.0398P)^2^+9.5171P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0987
_refine_ls_wR_factor_ref         0.1156
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4346
_reflns_number_total             6372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06483a2.cif
_cod_data_source_block           bq2_reprocess
_cod_depositor_comments
'Adding full bibliography for 1568667--1568672.cif.'
_cod_original_formula_sum        'C24.50 H24 B2 Br4 Cl N O'
_cod_database_code               1568670
_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. Shared sites
{C25, Cl3}
3. Restrained distances
 Cl2-C26
 1.78 with sigma of 0.02
 Cl3-C26
 1.77 with sigma of 0.02
 Cl2-C26 = Cl3-C26
 1.771 with sigma of 0.01
 Cl1-Cl4
 2.916 with sigma of 0.03
 Cl2-Cl3
 2.916 with sigma of 0.03
 Cl1-C25
 1.78 with sigma of 0.02
 Cl4-C25
 1.77 with sigma of 0.02
 Cl1-C25 = Cl4-C25
 1.771 with sigma of 0.01
 Cl2-Cl3
 2.92 with sigma of 0.04
 Cl1-Cl4
 2.92 with sigma of 0.04
4. Rigid bond restraints
 Cl2, Cl3, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl1, Cl4, C25
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Cl2 \\sim Cl3 \\sim C26: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1 \\sim Cl4 \\sim C25: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C25) = Uanis(Cl3)
Uanis(Cl1) = Uanis(C26)
Uanis(Cl4) = Uanis(C25)
Uanis(Cl2) = Uanis(C26)
6. Rigid body (RIGU) restrains
 Cl1, Cl4, C25
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl2, Cl3, C26
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Fixed Sof: Cl1(0.25) Cl4(0.25) C25(0.25) H25A(0.25) H25B(0.25) Cl2(0.25)
 Cl3(0.25) C26(0.25) H26A(0.25) H26B(0.25)
8.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C19(H19A,H19B), C18(H18A,H18B), C25(H25A,H25B), C26(H26A,H26B)
8.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C3(H3), C10(H10), C9(H9), C16(H16), C15(H15), C2(H2), C4(H4)
8.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C)
;
_shelx_res_checksum              7030
_shelx_hkl_checksum              49143
_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
;