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_1549416
_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         'C13 H18 B F4 N'
_chemical_formula_sum            'C13 H18 B F4 N'
_chemical_formula_weight         275.09
_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             2017-09-22
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_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            4
_cell_length_a                   8.48310(10)
_cell_length_b                   8.79060(10)
_cell_length_c                   17.8568(2)
_cell_measurement_reflns_used    18033
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2460
_cell_measurement_theta_min      4.9160
_cell_volume                     1331.61(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (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 0.998
_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   -115.00 -25.00   0.50    0.70    --  -49.12 -77.00 -90.00  180
  2  \w    -62.00  27.00   0.50    0.70    --  -49.12  19.00  60.00  178
  3  \w    -73.00  18.00   0.50    0.70    --  -49.12  77.00-150.00  182
  4  \w    -86.00   2.00   0.50    0.70    --  -70.00  57.00 -30.00  176
  5  \w    -88.00   2.00   0.50    0.70    --  -70.00 107.00  30.00  180
  6  \w    -83.00   6.00   0.50    0.70    --  -70.00  38.00-180.00  178
  7  \w   -115.00 -25.00   0.50    0.70    --  -49.12 -77.00 -30.00  180
  8  \w   -115.00 -25.00   0.50    0.70    --  -49.12 -77.00  90.00  180
  9  \w   -115.00 -25.00   0.50    0.70    --  -49.12 -77.00 120.00  180
 10  \w   -140.00 -82.00   0.50    0.70    --  -70.00 -99.00 120.00  116
 11  \w   -142.00 -54.00   0.50    0.70    --  -70.00 -57.00  30.00  176
 12  \w   -137.00 -71.00   0.50    0.70    --  -70.00 -77.00   0.00  132
 13  \w   -137.00 -46.00   0.50    0.70    --  -70.00 -77.00 -60.00  182
 14  \w   -115.00 -25.00   0.50    0.70    --  -49.12 -77.00-180.00  180
 15  \w   -137.00 -46.00   0.50    0.70    --  -70.00 -77.00-120.00  182
 16  \w     94.00 123.00   0.50    0.70    --  110.00 -19.00 -30.00   58
 17  \w     94.00 123.00   0.50    0.70    --  110.00 -19.00   0.00   58
 18  \w     94.00 123.00   0.50    0.70    --  110.00 -19.00  60.00   58
 19  \w     98.00 178.00   0.50    0.70    --  110.00  38.00   0.00  160
 20  \w    101.00 178.00   0.50    0.70    --  110.00 107.00  30.00  154
 21  \w     98.00 178.00   0.50    0.70    --  110.00  38.00 120.00  160
 22  \w     91.00 178.00   0.50    0.70    --  110.00 125.00   0.00  174
 23  \w     94.00 178.00   0.50    0.70    --  110.00  57.00 -60.00  168
 24  \w     98.00 178.00   0.50    0.70    --  110.00  38.00-180.00  160
 25  \w     94.00 123.00   0.50    0.70    --  110.00 -19.00-120.00   58
 26  \w     40.00 110.00   0.50    0.70    --  110.00 -99.00 -60.00  140
 27  \w     40.00 110.00   0.50    0.70    --  110.00 -99.00 -30.00  140
 28  \w     44.00 134.00   0.50    0.70    --  110.00 -77.00  60.00  180
 29  \w     39.00 122.00   0.50    0.70    --  110.00-125.00-120.00  166
 30  \w     40.00 110.00   0.50    0.70    --  110.00 -99.00  30.00  140
 31  \w     38.00  84.00   0.50    0.70    --  110.00 -57.00 -60.00   92
 32  \w     38.00  84.00   0.50    0.70    --  110.00 -57.00   0.00   92
 33  \w     38.00  84.00   0.50    0.70    --  110.00 -57.00  30.00   92
 34  \w     94.00 178.00   0.50    0.70    --  110.00  57.00  60.00  168
 35  \w     91.00 178.00   0.50    0.70    --  110.00 125.00-120.00  174
 36  \w     38.00  84.00   0.50    0.70    --  110.00 -57.00-180.00   92
 37  \w     39.00 122.00   0.50    0.70    --  110.00-125.00-180.00  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      0.0522585000
_diffrn_orient_matrix_UB_12      0.0460197000
_diffrn_orient_matrix_UB_13      -0.0794800000
_diffrn_orient_matrix_UB_21      0.0223470000
_diffrn_orient_matrix_UB_22      0.1653927000
_diffrn_orient_matrix_UB_23      0.0265041000
_diffrn_orient_matrix_UB_31      0.1724369000
_diffrn_orient_matrix_UB_32      -0.0352268000
_diffrn_orient_matrix_UB_33      0.0206586000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0396
_diffrn_reflns_av_unetI/netI     0.0160
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            27419
_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         79.713
_diffrn_reflns_theta_min         4.953
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.017
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.710
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (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    1.372
_exptl_crystal_description       block
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.163
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.298
_refine_diff_density_min         -0.178
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 1137 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.02(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     176
_refine_ls_number_reflns         2884
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0315
_refine_ls_R_factor_gt           0.0306
_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^)+(0.0466P)^2^+0.2258P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0813
_refine_ls_wR_factor_ref         0.0820
_reflns_Friedel_coverage         0.713
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                2794
_reflns_number_total             2884
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01486h1.cif
_cod_data_source_block           jb190917_2_1
_cod_depositor_comments
'Adding full bibliography for 1549414--1549418.cif.'
_cod_database_code               1549416
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C13H18BF4N
_reflns_odcompleteness_completeness 99.93
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.93 with sigma of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C7(H7A,H7B), C10(H10A,H10B), C11(H11A,H11B), C13(H13A,H13B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C9(H9)
3.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C)
;
_shelx_res_checksum              52815
_olex2_date_sample_data_collection 2017-09-20
_olex2_date_sample_submission    2017-09-19
_olex2_submission_original_sample_id jb190917_2_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 1.359
_oxdiff_exptl_absorpt_empirical_full_min 0.807