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_1549417
_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_formula_moiety         '2(C17 H18 B F4 N), C1.5 H3 O0.5'
_chemical_formula_sum            'C35.5 H39 B2 F8 N2 O0.5'
_chemical_formula_weight         675.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-11
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5375)
;
_audit_update_record
;
2018-03-29 deposited with the CCDC.
2018-05-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.9310(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.15540(10)
_cell_length_b                   14.81710(10)
_cell_length_c                   24.1310(2)
_cell_measurement_reflns_used    31188
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.7270
_cell_measurement_theta_min      3.4860
_cell_volume                     3265.82(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.23a (Rigaku OD, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.983
_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     85.00 173.00   0.50    0.50    --  107.75  77.00   0.00  176
  2  \w     91.00 178.00   0.50    0.50    --  107.75 125.00 150.00  174
  3  \w     95.00 178.00   0.50    0.50    --  107.75 119.00  81.00  166
  4  \w     97.00 178.00   0.50    0.50    --  107.75  19.00  90.00  162
  5  \w     98.00 178.00   0.50    0.50    --  107.75  38.00 150.00  160
  6  \w     97.00 178.00   0.50    0.50    --  107.75  19.00   0.00  162
  7  \w     85.00 173.00   0.50    0.50    --  107.75  77.00 -90.00  176
  8  \w     85.00 173.00   0.50    0.50    --  107.75  77.00-180.00  176
  9  \w     97.00 178.00   0.50    0.50    --  107.75  19.00-120.00  162
 10  \w     97.00 178.00   0.50    0.50    --  107.75  19.00 -90.00  162
 11  \w   -121.00   7.00   0.50    0.50    --  -50.21   0.00-150.00  256
 12  \w    -92.00  -5.00   0.50    0.50    --  -70.00  77.00 120.00  174
 13  \w    -85.00   1.00   0.50    0.50    --  -70.00  57.00-120.00  172
 14  \w    -60.00  25.00   0.50    0.50    --  -50.21  38.00-150.00  170
 15  \w     37.00  84.00   0.50    0.50    --  107.75 -57.00-120.00   94
 16  \w     37.00  84.00   0.50    0.50    --  107.75 -57.00 -60.00   94
 17  \w     43.00 130.00   0.50    0.50    --  107.75 -77.00  90.00  174
 18  \w   -141.00 -55.00   0.50    0.50    --  -70.00 -57.00 150.00  172
 19  \w   -141.00 -55.00   0.50    0.50    --  -70.00 -57.00  60.00  172
 20  \w   -141.00 -55.00   0.50    0.50    --  -70.00 -57.00 -30.00  172
 21  \w   -141.00 -55.00   0.50    0.50    --  -70.00 -57.00-120.00  172
 22  \w   -141.00 -55.00   0.50    0.50    --  -70.00 -57.00 -60.00  172
 23  \w   -121.00 -35.00   0.50    0.50    --  -50.21 -57.00   0.00  172
 24  \w   -141.00 -79.00   0.50    0.50    --  -70.00 -57.00 120.00  124
 25  \w   -121.00 -35.00   0.50    0.50    --  -50.21 -57.00  90.00  172
 26  \w     39.00 111.00   0.50    0.50    --  107.75 -99.00-120.00  144
 27  \w     38.00 121.00   0.50    0.50    --  107.75-125.00-150.00  166
 28  \w   -121.00 -35.00   0.50    0.50    --  -50.21 -57.00-180.00  172
 29  \w   -140.00 -75.00   0.50    0.50    --  -70.00-125.00-150.00  130
 30  \w   -139.00 -84.00   0.50    0.50    --  -70.00 -99.00 120.00  110
 31  \w     38.00 121.00   0.50    0.50    --  107.75-125.00 120.00  166
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0373498000
_diffrn_orient_matrix_UB_12      0.0637499000
_diffrn_orient_matrix_UB_13      0.0493806000
_diffrn_orient_matrix_UB_21      0.0075407000
_diffrn_orient_matrix_UB_22      -0.0814548000
_diffrn_orient_matrix_UB_23      0.0397848000
_diffrn_orient_matrix_UB_31      0.1642890000
_diffrn_orient_matrix_UB_32      -0.0106917000
_diffrn_orient_matrix_UB_33      -0.0085552000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0187
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            7917
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.104
_diffrn_reflns_theta_min         3.503
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.953
_exptl_absorpt_correction_T_max  0.920
_exptl_absorpt_correction_T_min  0.890
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.23a (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       block
_exptl_crystal_F_000             1408
_exptl_crystal_size_max          0.144
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.099
_refine_diff_density_max         0.295
_refine_diff_density_min         -0.407
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     515
_refine_ls_number_reflns         7917
_refine_ls_number_restraints     154
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0453
_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^)+(0.0640P)^2^+1.3423P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1196
_refine_ls_wR_factor_ref         0.1250
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6750
_reflns_number_total             7917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01486h1.cif
_cod_data_source_block           jb110817_1_1_twin1_hklf4
_cod_depositor_comments
'Adding full bibliography for 1549414--1549418.cif.'
_cod_original_formula_sum        'C35.50 H39 B2 F8 N2 O0.50'
_cod_database_code               1549417
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C37H34B2F10N2
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9102(16)
 0.0898(16)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N1A-H1A = N1C-H1C
 0.93 with sigma of 0.02
 C2E-C1E = C2F-C1E = C3E-C1E = C3F-C1E
 1.5 with sigma of 0.02
 O1F-C1E \\sim O1E-C1E
 with sigma of 0.02
 C2E-C3E \\sim C2F-C3F
 with sigma of 0.02
 C3E-C1E \\sim C3F-C1E \\sim C2F-C1E \\sim C2E-C1E
 with sigma of 0.02
 C2A-C1A \\sim C3A-C2A \\sim C3A-C2B \\sim C2B-C1A
 with sigma of 0.02
4. Restrained planarity
 C1E, O1F, C2F, C3F
 with sigma of 0.1
 C1E, O1E, C2E, C3E
 with sigma of 0.1
5. Rigid bond restraints
 C1E, O1F, C2F, C3F, O1E, C2E, C3E
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
Uanis(C3E) \\sim Ueq, Uanis(C3F) \\sim Ueq, Uanis(C1E) \\sim Ueq, Uanis(C2E)
\\sim Ueq, Uanis(C2F) \\sim Ueq, Uanis(O1E) \\sim Ueq, Uanis(O1F) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.01
7. Rigid body (RIGU) restrains
 C1E, O1F, C2F, C3F, O1E, C2E, C3E
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N1A, C1A, C3A, C4A, C2A, C2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(H1AC)=Sof(H1AD)=Sof(H3AC)=Sof(H3AD)=Sof(H15A)=Sof(F1B)=Sof(C2B)=Sof(H2BA)=
 Sof(H2BB)=1-FVAR(1)
 Sof(H1AA)=Sof(H1AB)=Sof(H3AA)=Sof(H3AB)=Sof(H9A)=Sof(F1A)=Sof(C2A)=Sof(H2AA)=
 Sof(H2AB)=FVAR(1)
 Sof(H9C)=Sof(F1D)=1-FVAR(2)
 Sof(H15C)=Sof(F1C)=FVAR(2)
 Sof(O1F)=Sof(C2F)=Sof(H2FA)=Sof(H2FB)=Sof(H2FC)=Sof(C3F)=Sof(H3FA)=Sof(H3FB)=
 Sof(H3FC)=0.5*(1-FVAR(4))
 Sof(O1E)=Sof(C2E)=Sof(H2EA)=Sof(H2EB)=Sof(H2EC)=Sof(C3E)=Sof(H3EA)=Sof(H3EB)=
 Sof(H3EC)=0.5*FVAR(4)
 Fixed Sof: C1E(0.5)
9.a Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C1A(H1AC,H1AD), C3A(H3AA,H3AB), C3A(H3AC,H3AD), C4A(H4AA,
 H4AB), C2A(H2AA,H2AB), C2B(H2BA,H2BB), C1C(H1CA,H1CB), C2C(H2CA,H2CB),
 C3C(H3CA,H3CB), C4C(H4CA,H4CB)
9.b Me refined with riding coordinates:
 C2F(H2FA,H2FB,H2FC), C3F(H3FA,H3FB,H3FC), C2E(H2EA,H2EB,H2EC), C3E(H3EA,H3EB,
 H3EC)
9.c Aromatic/amide H refined with riding coordinates:
 C7A(H7A), C8A(H8A), C9A(H9A), C10A(H10A), C11A(H11A), C13A(H13A), C14A(H14A),
 C15A(H15A), C16A(H16A), C17A(H17A), C7C(H7C), C8C(H8C), C9C(H9C), C10C(H10C),
 C11C(H11C), C13C(H13C), C14C(H14C), C15C(H15C), C16C(H16C), C17C(H17C)
;
_shelx_res_checksum              14921
_olex2_submission_original_sample_id jb110817_1_1
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.786
_oxdiff_exptl_absorpt_empirical_full_min 0.664
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2
_twin_special_details
;
Component 2 rotated by -164.5603\% 
 around [0.01 0.01 1.00] (reciprocal) or [0.23 0.02 0.97] (direct)
;