Regioselective C(sp<sup>3</sup>)-H borylation <i>via</i> a diarylboryl anion surrogate in sp<sup>2</sup>-sp<sup>3</sup> diboranes(5).
Mao, Xiaofeng; Zhang, Jie; Xie, Zuowei; Chemical science 16 (2025) 22314–22321; doi:10.1039/d5sc07180a

data_1576177
_publ_section_title
;
 Regioselective C(sp<sup>3</sup>)-H borylation <i>via</i> a diarylboryl
 anion surrogate in sp<sup>2</sup>-sp<sup>3</sup> diboranes(5).
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              22314
_journal_page_last               22321
_journal_paper_doi               10.1039/d5sc07180a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C35 H34 B2 K, 0.5(C4 H10 O)'
_chemical_formula_sum            'C37 H39 B2 K O0.5'
_chemical_formula_weight         552.40
_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             2022-12-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-07-26 deposited with the CCDC.	2025-11-04 downloaded from the CCDC.
;
_cell_angle_alpha                92.7200(10)
_cell_angle_beta                 109.5620(10)
_cell_angle_gamma                93.8790(10)
_cell_formula_units_Z            4
_cell_length_a                   12.8532(5)
_cell_length_b                   14.2497(5)
_cell_length_c                   18.1037(7)
_cell_measurement_reflns_used    9654
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      56.97
_cell_measurement_theta_min      2.71
_cell_volume                     3108.5(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT 2014'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker PHOTON III area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0513
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            72686
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         57.060
_diffrn_reflns_theta_min         2.260
_diffrn_source                   'microfocus Metaljet'
_diffrn_source_current           2.95
_diffrn_source_power             0.20608700000000002
_diffrn_source_type              'Incoatec Metaljet'
_diffrn_source_voltage           69.86
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.111
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.6672
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1036 before and 0.0562 after correction.
The Ratio of minimum to maximum transmission is 0.8882.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.180
_exptl_crystal_description       block
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.896
_refine_diff_density_min         -0.622
_refine_diff_density_rms         0.053
_refine_ls_extinction_coef       0.00092(19)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         12714
_refine_ls_number_restraints     145
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0434
_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^)+(0.0664P)^2^+1.5606P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1203
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11212
_reflns_number_total             12714
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07180a2.cif
_cod_data_source_block           '[2c]K'
_cod_depositor_comments
'Adding full bibliography for 1576174--1576180.cif.'
_cod_original_formula_sum        'C37 H39 B2 K O0.50'
_cod_database_code               1576177
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.776
_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
 C73A-C72A = C76A-C75A
 1.52 with sigma of 0.02
 O74A-C75A = O74A-C73A
 1.42 with sigma of 0.02
 C73A-C75A
 2.36 with sigma of 0.04
 O74A-C76A
 2.45 with sigma of 0.04
 O74A-C72A
 2.45 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O74 \\sim C72 \\sim C73 \\sim C75 \\sim C76 \\sim O74A \\sim C72A \\sim C73A
\\sim C75A \\sim C76A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C39 \\sim C40: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C73) = Uanis(C73A)
Uanis(C75) = Uanis(C75A)
Uanis(O74) = Uanis(O74A)
Uanis(C76) = Uanis(C76A)
Uanis(C72) = Uanis(C72A)
4. Others
 Sof(O74A)=Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C73A)=Sof(H73C)=
 Sof(H73D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C76A)=Sof(H76D)=Sof(H76E)=
 Sof(H76F)=1-FVAR(1)
 Sof(O74)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C73)=Sof(H73A)=Sof(H73B)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C5(H5), C10(H10)
5.b Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C75(H75A,H75B), C73A(H73C,H73D), C75A(H75C,H75D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C8(H8), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C20(H20), C23(H23), C24(H24), C28(H28), C29(H29),
  C30(H30), C31(H31), C32(H32), C36(H36), C38(H38), C39(H39), C40(H40),
 C43(H43), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C54(H54),
  C55(H55), C56(H56), C57(H57), C59(H59), C60(H60), C62(H62), C63(H63),
 C68(H68), C69(H69), C70(H70), C71(H71)
5.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C27(H27A,H27B,H27C), C35(H35A,H35B,H35C), C42(H42A,H42B,
 H42C), C46(H46A,H46B,H46C), C53(H53A,H53B,H53C), C64(H64A,H64B,H64C), C67(H67A,
 H67B,H67C), C72(H72A,H72B,H72C), C76(H76A,H76B,H76C), C72A(H72D,H72E,H72F),
 C76A(H76D,H76E,H76F)
;
_shelx_res_checksum              19408
_olex2_submission_special_instructions 'No special instructions were received'