Enantioselective reduction of N-alkyl ketimines with frustrated Lewis pair catalysis using chiral borenium ions
Mercea, Dan; Howlett, Michael; Piascik, Adam D.; Scott, Daniel; Steven, Alan; Ashley, Andrew Edward; Fuchter, Matthew; Chemical Communications  (2019) –; doi:10.1039/C9CC02900A

data_7123509
_publ_section_title
;
 Enantioselective reduction of N-alkyl ketimines with frustrated Lewis
 pair catalysis using chiral borenium ions
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC02900A
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C2 F6 N O4 S2, C21 H34 B N2 O2'
_chemical_formula_sum            'C23 H34 B F6 N3 O6 S2'
_chemical_formula_weight         637.46
_chemical_properties_physical    Moisture-sensitive
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_symmetry_space_group_name_Hall  'P 32'
_symmetry_space_group_name_H-M   'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-12
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-13 deposited with the CCDC.    2019-05-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            3
_cell_length_a                   10.6336(3)
_cell_length_b                   10.6336(3)
_cell_length_c                   22.5220(7)
_cell_measurement_reflns_used    2381
_cell_measurement_temperature    173.05(10)
_cell_measurement_theta_max      26.6310
_cell_measurement_theta_min      3.4810
_cell_volume                     2205.46(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (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      173.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0382
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.857
_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    -52.00  31.00   1.00    7.05    --   14.43 -57.00 120.00   83
  2  \w    -10.00  82.00   1.00    7.05    --   14.43  77.00  30.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0019300000
_diffrn_orient_matrix_UB_12      0.0644970000
_diffrn_orient_matrix_UB_13      -0.0059950000
_diffrn_orient_matrix_UB_21      -0.0764673000
_diffrn_orient_matrix_UB_22      -0.0383441000
_diffrn_orient_matrix_UB_23      0.0038375000
_diffrn_orient_matrix_UB_31      0.0091603000
_diffrn_orient_matrix_UB_32      0.0173980000
_diffrn_orient_matrix_UB_33      0.0306718000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0199
_diffrn_reflns_av_unetI/netI     0.0494
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            8361
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.802
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.206
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.261
_exptl_absorpt_correction_T_max  0.957
_exptl_absorpt_correction_T_min  0.915
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_description       block
_exptl_crystal_F_000             996
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: 1,2-DFB, pentane'
_exptl_crystal_size_max          0.575
_exptl_crystal_size_mid          0.299
_exptl_crystal_size_min          0.219
_refine_diff_density_max         0.455
_refine_diff_density_min         -0.392
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 1877 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     446
_refine_ls_number_reflns         5821
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0703
_refine_ls_R_factor_gt           0.0554
_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^)+(0.0441P)^2^+1.2751P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1139
_refine_ls_wR_factor_ref         0.1244
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.748
_reflns_number_gt                4911
_reflns_number_total             5821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc02900a2.cif
_cod_data_source_block           mf1803
_cod_original_cell_volume        2205.45(14)
_cod_database_code               7123509
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C23 H34 B F6 N3 O6 S2'
_chemical_oxdiff_usercomment     DM3-429
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Fixed Sof: F1A(0.75) O4A(0.75) O3A(0.75) F3A(0.75) F2A(0.75) F6B(0.25)
 N3A(0.75) F5A(0.75) O3B(0.25) O4B(0.25) F3B(0.25) N3B(0.25) F1B(0.25)
 F2B(0.25) F5B(0.25) F6A(0.75)
3.a Ternary CH refined with riding coordinates:
 C18(H18), C2(H2), C3(H3), C10(H10), C11(H11), C14(H14)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C19(H19A,H19B), C6(H6A,H6B), C9(H9A,H9B),
 C21(H21A,H21B), C20(H20A,H20B), C15(H15A,H15B)
3.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C4(H4A,H4B,H4C), C13(H13A,H13B,H13C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              11733
_olex2_date_sample_data_collection 2018-06-12
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.068
_oxdiff_exptl_absorpt_empirical_full_min 0.946