Facile synthesis of α-aminoboronic acids from amines and potassium acyltrifluoroborates (KATs) <i>via</i> trifluoroborate-iminiums (TIMs).
Shiro, Tomoya; Schuhmacher, Anne; Jackl, Moritz K.; Bode, Jeffrey W.; Chemical science 9 (2018) 5191–5196; doi:10.1039/c8sc01486h

data_1549414
_publ_section_title
;
 Facile synthesis of \a-aminoboronic acids from amines and potassium
 acyltrifluoroborates (KATs) <i>via</i> trifluoroborate-iminiums (TIMs).
;
_journal_issue                   23
_journal_name_full               'Chemical science'
_journal_page_first              5191
_journal_page_last               5196
_journal_paper_doi               10.1039/c8sc01486h
_journal_volume                  9
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C11 H12 B Br F3 N'
_chemical_formula_sum            'C11 H12 B Br F3 N'
_chemical_formula_weight         305.94
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-10
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2018-03-29 deposited with the CCDC.
2018-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.442(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.1247(8)
_cell_length_b                   11.1474(11)
_cell_length_c                   11.9275(12)
_cell_measurement_reflns_used    9930
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      28.28
_cell_measurement_theta_min      2.50
_cell_volume                     1213.2(2)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0261
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            22040
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.291
_diffrn_reflns_theta_min         2.501
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms high brilliance'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.401
_exptl_absorpt_correction_T_max  0.7302
_exptl_absorpt_correction_T_min  0.5817
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1262 before and 0.0655 after correction.
The Ratio of minimum to maximum transmission is 0.7966.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.675
_exptl_crystal_description       plate
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.343
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 2415 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.017(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.908
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     335
_refine_ls_number_reflns         5908
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      0.918
_refine_ls_R_factor_all          0.0219
_refine_ls_R_factor_gt           0.0191
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0384
_refine_ls_wR_factor_ref         0.0389
_reflns_Friedel_coverage         0.871
_reflns_Friedel_fraction_full    0.967
_reflns_Friedel_fraction_max     0.962
_reflns_number_gt                5500
_reflns_number_total             5908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01486h1.cif
_cod_data_source_block           jb080616_1_1_0m
_cod_depositor_comments
'Adding full bibliography for 1549414--1549418.cif.'
_cod_database_code               1549414
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.535
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 F2-B1 \\sim F2A-B1 \\sim F3-B1 \\sim F3A-B1 \\sim F1-B1 \\sim F1A-B1
 with sigma of 0.02
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F1A-F2A \\sim F2A-F3A \\sim F3A-F1A
 with sigma of 0.02
3. Rigid bond restraints
 F3, F2, F1, B1, F2A, F3A, F1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2) \\sim Ueq, Uanis(F2A)
\\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F3A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 F3, F2, F1, B1, F2A, F3A, F1A, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(1)
 Sof(F3)=Sof(F2)=Sof(F1)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C19(H19A,H19B), C9(H9A,H9B), C22(H22A,H22B), C20(H20A,H20B),
 C11(H11A,H11B), C10(H10A,H10B), C21(H21A,H21B)
7.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C13(H13), C6(H6), C17(H17), C14(H14), C3(H3), C16(H16), C2(H2)
;
_shelx_res_checksum              25105
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-06-08
_olex2_date_sample_submission    2016-06-07
_olex2_submission_original_sample_id jb080616_1_1
_olex2_submission_special_instructions 'No special instructions were received'