Regioselective 1,4-Hydroboration of Pyridines Catalyzed by an Acid-Initiated Boronium Cation
Keyzer, Evan; Kang, Sky; Hanf, Schirin; Wright, Dominic S.; Chem. Commun.  (2017) –; doi:10.1039/C7CC04988A

data_7120483
_publ_section_title
;
 Regioselective 1,4-Hydroboration of Pyridines Catalyzed by an
 Acid-Initiated Boronium Cation
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC04988A
_journal_year                    2017
_chemical_formula_moiety         'C16 H22 B N2 O2, C24 H20 B'
_chemical_formula_sum            'C40 H42 B2 N2 O2'
_chemical_formula_weight         604.37
_chemical_properties_physical    ', Air-sensitive,Moisture-sensitive'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-05-04
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_audit_update_record
;
2017-05-10 deposited with the CCDC.
2017-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                95.1220(13)
_cell_angle_beta                 102.8720(13)
_cell_angle_gamma                95.0690(14)
_cell_formula_units_Z            2
_cell_length_a                   10.5637(3)
_cell_length_b                   10.8714(3)
_cell_length_c                   15.2958(4)
_cell_measurement_reflns_used    9985
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      66.75
_cell_measurement_theta_min      4.11
_cell_volume                     1694.99(8)
_computing_cell_refinement       'SAINT (Bruker, 2014)'
_computing_data_collection       'APEX3 (Bruker, 2015)'
_computing_data_reduction        SAINT
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  SHELXL
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      180.0
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_device_type  'Bruker D8-QUEST PHOTON-100'
_diffrn_measurement_method       'Thin slice \w and \f scans'
_diffrn_radiation_source         'Incoatec I\mS Cu microsource'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            32118
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.916
_diffrn_reflns_theta_max         66.916
_diffrn_reflns_theta_min         2.982
_exptl_absorpt_coefficient_mu    0.550
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.4465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Bruker, 2014)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_description       block
_exptl_crystal_F_000             644
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.221
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         5953
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0800
_refine_ls_R_factor_gt           0.0604
_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^)+(0.0510P)^2^+1.2568P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1381
_refine_ls_wR_factor_ref         0.1525
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4679
_reflns_number_total             5953
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc04988a2.cif
_cod_data_source_block           DW_B2_0282
_cod_database_code               7120483
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_min   0.699
_shelx_estimated_absorpt_t_max   0.973
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C39-C43 = C39-C44 = C40-C42 = C40-C41 = C39-C40
 1.54 with sigma of 0.01
 C45-C49 = C45-C50 = C46-C48 = C46-C47 = C45-C46
 1.54 with sigma of 0.01
 C43-C44 = C41-C42
 2.51 with sigma of 0.02
 C49-C50 = C47-C48
 2.51 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq,
Uanis(C46) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C45)=Sof(C46)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=
 Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=
 Sof(H50B)=Sof(H50C)=1-FVAR(1)
 Sof(C39)=Sof(C40)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=
 Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=
 Sof(H44B)=Sof(H44C)=FVAR(1)
5.a Me refined with riding coordinates:
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C)
5.b Aromatic/amide H refined with riding coordinates:
 C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7),
 C8(H8), C9(H9), C10(H10), C11(H11), C14(H14), C15(H15), C16(H16), C17(H17),
 C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24)
;
_shelx_res_checksum              62861
_shelx_hkl_checksum              76521
_olex2_submission_special_instructions 'No special instructions were received'