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_1549418
_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 H14 B F4 N'
_chemical_formula_sum            'C11 H14 B F4 N'
_chemical_formula_weight         247.04
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.85970(10)
_cell_length_b                   11.13680(10)
_cell_length_c                   19.4080(2)
_cell_measurement_reflns_used    55936
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.5940
_cell_measurement_theta_min      4.4830
_cell_volume                     2347.25(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28c (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28c (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28c (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 0.996
_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    -96.00 -27.00   0.50    0.10    --  -26.00 161.00  50.74  138
  2  \w    -48.00 -22.00   0.50    0.10    --   14.00 151.00 -48.85   52
  3  \w    -51.00  40.00   0.50    0.10    --  -26.00  82.00-128.81  182
  4  \w    -95.00  -9.00   0.50    0.10    --  -70.00 125.00-180.00  172
  5  \w     -7.00  22.00   0.50    0.10    --   26.00  99.00-128.12   58
  6  \w     85.00 167.00   0.50    0.10    --  107.75  77.00-150.00  164
  7  \w     87.00 173.00   0.50    0.10    --  107.75  72.00  -1.00  172
  8  \w     99.00 125.00   0.50    0.10    --  107.75  38.00  60.00   52
  9  \w    153.00 178.00   0.50    0.10    --  107.75  38.00  60.00   50
 10  \w     59.00 120.00   0.50    0.10    --   50.21 178.00  90.00  122
 11  \w     15.00  44.00   0.50    0.10    --   38.00  79.00 -97.92   58
 12  \w    -73.00  15.00   0.50    0.10    --  -50.21  77.00  90.00  176
 13  \w     15.00  44.00   0.50    0.10    --   38.00  79.00 100.99   58
 14  \w     29.00 117.00   0.50    0.10    --   50.00  73.00  31.39  176
 15  \w     37.00  83.00   0.50    0.10    --  107.75 -57.00   0.00   92
 16  \w     46.00  72.00   0.50    0.10    --  107.75 -77.00 -30.00   52
 17  \w    103.00 130.00   0.50    0.10    --  107.75 -77.00 -30.00   54
 18  \w   -137.00 -50.00   0.50    0.10    --  -70.00 -71.00 143.24  174
 19  \w   -137.00 -50.00   0.50    0.10    --  -70.00 -71.00 -47.98  174
 20  \w   -138.00 -51.00   0.50    0.10    --  -70.00 -67.00-176.29  174
 21  \w     40.00 125.00   0.50    0.10    --   50.21  38.00-180.00  170
 22  \w     34.00 121.00   0.50    0.10    --   54.00  72.00 -52.36  174
 23  \w     38.00 125.00   0.50    0.10    --   58.00  72.00 142.87  174
 24  \w     38.00 125.00   0.50    0.10    --   58.00  72.00-163.41  174
 25  \w     38.00 125.00   0.50    0.10    --   58.00  72.00-110.48  174
 26  \w     42.00 130.00   0.50    0.10    --   62.00  70.00 -69.80  176
 27  \w     46.00 133.00   0.50    0.10    --   66.00  72.00  49.83  174
 28  \w     45.00 133.00   0.50    0.10    --   66.00  73.00-145.21  176
 29  \w     49.00 137.00   0.50    0.10    --   70.00  73.00 -61.66  176
 30  \w     53.00 141.00   0.50    0.10    --   74.00  73.00  97.92  176
 31  \w     53.00 141.00   0.50    0.10    --   74.00  73.00 -51.83  176
 32  \w     55.00 142.00   0.50    0.10    --   74.00  69.00 -18.54  174
 33  \w     64.00 151.00   0.50    0.10    --   82.00  65.00 115.35  174
 34  \w     68.00  95.00   0.50    0.10    --   82.00  58.00   6.21   54
 35  \w     70.00 114.00   0.50    0.10    --   86.00  60.00-170.53   88
 36  \w     93.00 127.00   0.50    0.10    --  107.75  57.00-150.00   68
 37  \w     85.00 173.00   0.50    0.10    --  107.75  77.00  30.00  176
 38  \w     85.00 172.00   0.50    0.10    --  107.75  77.00-120.00  174
 39  \w    122.00 173.00   0.50    0.10    --  107.75  77.00  90.00  102
 40  \w     85.00 117.00   0.50    0.10    --  107.75  77.00  90.00   64
 41  \w     86.00 171.00   0.50    0.10    --  107.75  77.00 -60.00  170
 42  \w    146.00 173.00   0.50    0.10    --  107.75  77.00 -90.00   54
 43  \w    132.00 171.00   0.50    0.10    --  107.75  71.00-175.22   78
 44  \w     86.00 131.00   0.50    0.10    --  107.75  77.00 -90.00   90
 45  \w    134.00 160.00   0.50    0.10    --  107.75  77.00   0.00   52
 46  \w    109.00 138.00   0.50    0.10    --  107.75  38.00 -90.00   58
 47  \w    143.00 174.00   0.50    0.10    --  107.75  38.00 -90.00   62
 48  \w     88.00 117.00   0.50    0.10    --  107.75  71.00-175.22   58
 49  \w     85.00 111.00   0.50    0.10    --  107.75  77.00   0.00   52
 50  \w    118.00 167.00   0.50    0.10    --  107.75  77.00 120.00   98
 51  \w     85.00 113.00   0.50    0.10    --  107.75  77.00 120.00   56
 52  \w     85.00 173.00   0.50    0.10    --  107.75  77.00  60.00  176
 53  \w     94.00 171.00   0.50    0.10    --  107.75  57.00 150.00  154
 54  \w     97.00 130.00   0.50    0.10    --  107.75  57.00 120.00   66
 55  \w     98.00 144.00   0.50    0.10    --  107.75  57.00-180.00   92
 56  \w     86.00 173.00   0.50    0.10    --  107.75  77.00 -30.00  174
 57  \w     94.00 119.00   0.50    0.10    --  107.75-125.00-180.00   50
 58  \w     62.00  87.00   0.50    0.10    --  107.75-125.00-180.00   50
 59  \w     46.00  76.00   0.50    0.10    --  107.75 -99.00-180.00   60
 60  \w     39.00 109.00   0.50    0.10    --  107.75 -99.00  30.00  140
 61  \w     40.00 106.00   0.50    0.10    --  107.75 -99.00 120.00  132
 62  \w     41.00  67.00   0.50    0.10    --  107.75 -99.00 -60.00   52
 63  \w     45.00 110.00   0.50    0.10    --  107.75 -99.00-150.00  130
 64  \w     40.00  85.00   0.50    0.10    --  107.75 -99.00-120.00   90
 65  \w     59.00 121.00   0.50    0.10    --  107.75-125.00   0.00  124
 66  \w     86.00 111.00   0.50    0.10    --  107.75 -99.00 -60.00   50
 67  \w   -125.00 -40.00   0.50    0.10    --  -50.21 -19.00 150.00  170
 68  \w   -137.00 -49.00   0.50    0.10    --  -70.00 -72.00  45.93  176
 69  \w   -138.00 -51.00   0.50    0.10    --  -70.00 -69.00  94.84  174
 70  \w   -137.00 -50.00   0.50    0.10    --  -70.00 -70.00-118.44  174
 71  \w   -138.00 -51.00   0.50    0.10    --  -70.00 -68.00   3.58  174
 72  \w   -136.00 -49.00   0.50    0.10    --  -70.00 -73.00 169.70  174
 73  \w   -137.00 -49.00   0.50    0.10    --  -70.00 -72.00-131.00  176
 74  \w   -136.00 -49.00   0.50    0.10    --  -70.00 -73.00 -17.75  174
 75  \w   -137.00 -49.00   0.50    0.10    --  -70.00 -72.00 118.48  176
 76  \w   -136.00 -49.00   0.50    0.10    --  -70.00 -73.00  84.12  174
 77  \w   -139.00 -53.00   0.50    0.10    --  -70.00 -64.00  53.08  172
;
_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      -0.0107230000
_diffrn_orient_matrix_UB_12      -0.1304905000
_diffrn_orient_matrix_UB_13      -0.0256403000
_diffrn_orient_matrix_UB_21      0.0854941000
_diffrn_orient_matrix_UB_22      -0.0415860000
_diffrn_orient_matrix_UB_23      0.0586429000
_diffrn_orient_matrix_UB_31      -0.1127196000
_diffrn_orient_matrix_UB_32      -0.0193307000
_diffrn_orient_matrix_UB_33      0.0469483000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0532
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            89056
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.169
_diffrn_reflns_theta_min         4.557
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.092
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.530
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28c (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    1.398
_exptl_crystal_description       block
_exptl_crystal_F_000             1024
_exptl_crystal_size_max          0.214
_exptl_crystal_size_mid          0.185
_exptl_crystal_size_min          0.131
_refine_diff_density_max         0.310
_refine_diff_density_min         -0.176
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 2016 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.05(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     313
_refine_ls_number_reflns         5049
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0304
_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^)+(0.0352P)^2^+0.6082P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0743
_refine_ls_wR_factor_ref         0.0753
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                4859
_reflns_number_total             5049
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01486h1.cif
_cod_data_source_block           jb120817_1_1
_cod_depositor_comments
'Adding full bibliography for 1549414--1549418.cif.'
_cod_database_code               1549418
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C22H28B2F8N2
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 N1A-H1A = N1B-H1B
 0.93 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 C1A(H1AA), C1B(H1BA)
3.b Secondary CH2 refined with riding coordinates:
 C8A(H8AA,H8AB), C9A(H9AA,H9AB), C10A(H10A,H10B), C11A(H11A,H11B), C8B(H8BA,
 H8BB), C9B(H9BA,H9BB), C10B(H10C,H10D), C11B(H11C,H11D)
3.c Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C6A(H6A), C7A(H7A), C3B(H3B), C4B(H4B), C6B(H6B), C7B(H7B)
;
_shelx_res_checksum              41719
_olex2_submission_original_sample_id jb120817_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 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.837