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_1568671
_publ_section_title
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 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         'C24 H26 B N O, C H Cl3'
_chemical_formula_sum            'C25 H27 B Cl3 N O'
_chemical_formula_weight         474.63
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-11-22 deposited with the CCDC.	2023-03-15 downloaded from the CCDC.
;
_cell_angle_alpha                86.088(4)
_cell_angle_beta                 72.721(3)
_cell_angle_gamma                77.089(4)
_cell_formula_units_Z            4
_cell_length_a                   11.9253(5)
_cell_length_b                   13.1059(8)
_cell_length_c                   16.0617(6)
_cell_measurement_reflns_used    9651
_cell_measurement_temperature    120.1(5)
_cell_measurement_theta_max      28.8790
_cell_measurement_theta_min      3.7630
_cell_volume                     2336.4(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.1(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.907
_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    -88.00 -26.00   1.00   20.00    --  -15.66 163.00-144.00   62
  2  \w    -64.00   7.00   1.00   20.00    --  -15.66 116.00  67.00   71
  3  \w     26.00  90.00   1.00   20.00    --   17.54-163.00-169.00   64
  4  \w     -7.00  66.00   1.00   20.00    --   17.54-116.00 -20.00   73
  5  \w    -88.00 -35.00   1.00   20.00    --  -15.66 178.00 -60.00   53
  6  \w    -83.00   1.00   1.00   20.00    --  -15.66 -57.00  90.00   84
  7  \w    -32.00  52.00   1.00   20.00    --  -15.66  57.00-150.00   84
  8  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00  90.00   48
  9  \w     -9.00  39.00   1.00   20.00    --   17.54  77.00-120.00   48
 10  \w    -52.00  36.00   1.00   20.00    --   17.54 -38.00  60.00   88
 11  \w      1.00  85.00   1.00   20.00    --   17.54  57.00 -90.00   84
 12  \w      1.00  85.00   1.00   20.00    --   17.54  57.00   0.00   84
 13  \w    -88.00 -35.00   1.00   20.00    --  -15.66 178.00  30.00   53
 14  \w    -20.00  56.00   1.00   20.00    --   17.54 -99.00  60.00   76
 15  \w     -1.00  87.00   1.00   20.00    --   17.54  38.00 150.00   88
 16  \w    -20.00  56.00   1.00   20.00    --   17.54 -99.00-150.00   76
 17  \w     -1.00  87.00   1.00   20.00    --   17.54  38.00-120.00   88
 18  \w     35.00  90.00   1.00   20.00    --   17.54-178.00  90.00   55
 19  \w    -39.00  44.00   1.00   20.00    --   17.54 -77.00-120.00   83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0095200000
_diffrn_orient_matrix_UB_12      0.0504742000
_diffrn_orient_matrix_UB_13      0.0049900000
_diffrn_orient_matrix_UB_21      -0.0618960000
_diffrn_orient_matrix_UB_22      0.0215766000
_diffrn_orient_matrix_UB_23      0.0057538000
_diffrn_orient_matrix_UB_31      -0.0119648000
_diffrn_orient_matrix_UB_32      -0.0083547000
_diffrn_orient_matrix_UB_33      0.0456170000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0860
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.907
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            18790
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.907
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.412
_diffrn_reflns_theta_min         3.322
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.410
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95713
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
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    1.349
_exptl_crystal_description       plate
_exptl_crystal_F_000             992
_exptl_crystal_recrystallization_method 'Crystallised from chloroform at 4 C.'
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.245
_exptl_crystal_size_min          0.109
_refine_diff_density_max         0.581
_refine_diff_density_min         -0.550
_refine_diff_density_rms         0.064
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.961
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     568
_refine_ls_number_reflns         18790
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.961
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0489P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0953
_refine_ls_wR_factor_ref         0.1004
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12710
_reflns_number_total             18790
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9465\% 
around [0.00 1.00 -0.00] (reciprocal) or [-0.24 0.97 -0.00] (direct)
;
_cod_data_source_file            d2sc06483a2.cif
_cod_data_source_block           mu699_boh_b_twin_refinalized_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1568667--1568672.cif.'
_cod_database_code               1568671
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N O'
_chemical_oxdiff_usercomment     '120 K'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5659(6)
 0.4341(6)
2. 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, All O(H) groups
3.a Ternary CH refined with riding coordinates:
 C49(H49), C50(H50)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C20(H20A,H20B), C25(H25A,H25B),
 C26(H26A,H26B), C27(H27A,H27B), C44(H44A,H44B)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C15(H15), C16(H16), C17(H17),
 C30(H30), C31(H31), C35(H35), C36(H36), C37(H37), C39(H39), C40(H40), C41(H41)
3.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
3.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
;
_shelx_res_checksum              84422
_shelx_hkl_checksum              23033
_olex2_exptl_crystal_mounting_method
'The crystal was mounted in oil on MITEGEN holder.'
_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 1.144
_oxdiff_exptl_absorpt_empirical_full_min 0.927
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2